200904283 九、發明說明 【發明所屬之技術領域] 本發明關於金屬膜轉印用薄膜、金屬膜之轉印方法及 電路基板之製造方法，尤其關於在撓性印刷配線板、多層 印刷配線板等的電路基板之製造中，適用於在絕緣層表面 上形成當作導體層形成用的片層之金屬層的金屬膜轉印用 薄膜’由該薄膜來轉印金屬膜的方法，及使用該薄膜的電 路基板之製造方法。 【先前技術】 各種電子機器中所廣泛使用的多層印刷配線板、撓性 印刷配線板等之電路基板，爲了電子機器的小型化、高機 能化，而被要求層的薄型化或電路的微細配線化。因此， 作爲其製造方法，例如已知有於內層電路基板上，藉由黏 著薄膜來層合硬化性樹脂組成物，使該硬化性樹脂組成物 硬化以形成絕緣層後，以鹼性過錳酸鉀溶液等的氧化劑將 該絕緣層粗化，於該粗面上藉由無電解鍍敷來形成鍍片層 ，接著藉由電解鍍敷以形成導體層的半加法。此處，於該 方法中爲了得到密接強度高的導體層，如上述地需要氧化 劑將絕緣層表面粗化（在表面形成凹凸），而在與導體層 之間得到錨固效果，但於電路形成時藉由蝕刻來去除不要 的鍍片層時，難以去除錨固部分的片層，以能充分去除錨 固部分的片層之條件來進行飩刻時，配線圖型的溶解係顯 著化，發生成爲微細配線化的妨礙之問題。 -5- 200904283 因此，作爲解決如此問題的方法，嘗試藉由轉印而在 基板上形成金屬膜層的方法。此係爲在支持體上隔著脫模 層藉由蒸鍍等來形成金屬膜層以製作轉印用薄膜，將該轉 印用薄膜的金屬膜層轉印到基扳上的樹脂組成物層（絕緣 層）表面或預浸體表面，於所轉印的金屬膜層上藉由鍍敷 等來形成導體層的方法。例如，有報告使用一採用氟樹脂 、烯烴樹脂、聚乙烯醇樹脂當作脫模層的轉印用薄膜之方 法（專利文獻1)、使用一採用含有丙烯酸樹脂或蜜胺樹 脂等的黏著樹脂之黏著劑當作脫模層的轉印用薄膜之方法 (專利文獻2 )等。 [專利文獻1]特開2004-230729號公報 [專利文獻2]特開2002_324969號公報 【發明內容】 (發明所欲解決的問題） 然而，於專利文獻1的實施例中，由在脫模層中使用 氟樹脂的轉印用薄膜，隔著環氧系接著劑將銅膜轉印到聚 醯亞胺薄膜上，但爲了得到良好的轉印性，環氧系接著劑 與銅膜之間必須有高黏著性，對黏著性相對低的被附體（ 基板上的樹脂組成物層或預浸體等）之表面的轉印一般係 困難。又，於轉印時，藉由使樹脂組成物層或預浸體硬化 ’雖然可提高與金屬膜層的黏著性，但本發明人們嘗試以 使用附有氟樹脂系脫模層的聚對苯二甲酸乙二酯（PET ) 薄膜之轉印用薄膜，對樹脂組成物層進行銅膜的轉印，結 -6- 200904283 果從硬化的樹脂組成物層上所黏著的銅膜，剝離PET薄膜 的剝離性係差，均勻的銅膜之轉印係困難。又，本發明人 們嘗試如專利文獻1中所揭示地，使用聚乙烯醇樹脂於脫 模層，對樹脂組成物層進行銅膜的轉印，但從硬化的樹脂 組成物層上所黏著的銅膜，剝離p E T薄膜係困難。另外， 本發明人們嘗試如專利文獻2中所揭示地，藉由附有丙稀 酸樹脂系脫模層的PET薄膜及附有蜜胺樹脂系脫模層的 PET薄膜，對樹脂組成物層進行銅膜的轉印，但從硬化的 樹脂組成物層上所黏著的銅膜，剝離P E T薄膜的剝離性仍 然差，均勻銅膜的轉印係困難。 因此，本發明所欲解決的問題爲提供具有優異的金屬 膜層轉印性之金屬膜轉印用薄膜，以及提供使用該金屬膜 轉印用薄膜來有效率地製造電路基板之方法。 (解決問題的手段） 本發明人們爲了解決上述課題，進行專心致力的檢討 ，結果發現藉由在金屬膜轉印用薄膜的脫模層採用水溶性 纖維素樹脂層、水溶性聚酯樹脂層或水溶性丙烯酸樹脂層 ，例如於電路基板製造步驟中’於基板上的硬化性樹脂組 成物層上，以金屬膜層接觸樹脂組成物層表面的方式’重 疊層合金屬膜轉印用薄膜’將樹脂組成物層硬化’則可在 與脫模層的界面中容易剝離支持體層’而且之後藉由水溶 液來去除金屬膜層上所存在的脫模層’則金屬膜層沒有不 均，而可有效率地轉印，均勻的金屬膜層轉印係成爲可能 200904283 ’完成本發明。η卩，本發明包含以下的內容。 (1) 一種金屬膜轉印用薄膜，其特徵爲具有：支持 體層，及在該支持體層上之由水溶性纖維素樹脂、水溶性 聚酯樹脂及水溶性丙烯酸樹脂所選出的1種以上之水溶性 高分子所形成的脫模層，以及在該脫模層上所形成的金屬 膜層。 (2 )如上述（1 )記載的金屬膜轉印用薄膜，其中脫 模層係水溶性纖維素樹脂層。 (3 )如上述（1 )或（2 )記載的金屬膜轉印用薄膜 ，其中水溶性纖維素樹脂層係由羥丙基甲基纖維素苯二甲 酸酯、羥丙基甲基纖維素醋酸酯琥珀酸酯及羥丙基甲基纖 維素醋酸酯苯二甲酸酯所組成族群所選出的1種或2種以 上所構成。 (4 )如上述（1 )〜（3 )中任一項記載的金屬膜轉 印用薄膜，其中支持體層係塑膠薄膜。 (5 )如上述（1 )〜（3 )中任一項記載的金屬膜轉 印用薄膜，其中支持體層係聚對苯二甲酸乙二酯薄膜。 (6 )如上述（1 )〜（5 )中任一項記載的金屬膜轉 印用薄膜，其中金屬膜層係由鉻、鎳、鈦、鎳-鉻合金、 鋁、金、銀及銅所組成族群所選出的金屬所形成的1層或 2層以上之層。 (7)如上述（1)〜（5)中任一項記載的金屬膜轉 印用薄膜，其中金屬膜層係由銅所形成。 (8 )如上述（1 )〜（5 )中任一項記載的金屬膜轉 -8- 200904283 印用薄膜，其中金屬膜層係在脫模層上依順序形成有銅層 及鉻層、鎳-鉻合金層或鈦層者。 (9 )如上述（1 )〜（8 )中任一項記載的金屬膜轉 印用薄膜，其中金屬膜層係藉由蒸鍍法或/及濺鍍法形成 者。 (1 〇 )如上述（1 )〜（9 )中任一項記載的金屬膜轉 印用薄膜，其中支持體層的層厚爲ΙΟμιη〜70μιη。 (11)如上述（1)〜（10)中任一項記載的金屬膜 轉印用薄膜，其中脫模層的層厚爲Ο.ίμιη〜20μιη。 (1 2 )如上述（1 )〜（1 0 )中任一項記載的金屬膜 轉印用薄膜，其中脫模層的層厚爲〇.2μιη〜5μιη。 (1 3 )如上述（1 )〜（1 2 )中任一項記載的金屬膜 轉印用薄膜，其中金屬膜層的層厚爲50nm〜5000nm。 (14 )如上述（1 )〜（12 )中任一項記載的金屬膜 轉印用薄膜，其中金屬膜層的層厚爲50nm〜lOOOnm。 (15) —種金屬膜層之轉印方法，至少包含：於表層 由硬化性樹脂組成物所成的被附體上，以金屬膜層接觸被 附體之表面的方式，重疊層合上述（1)〜（14)中任一 項記載的金屬膜轉印用薄膜，將硬化性樹脂組成物硬化之 步驟，剝離支持體層之步驟，及以水溶液來溶解去除金屬 膜層上所存在的脫模層之步驟。 (16) —種電路基板之製造方法，包含：於基板上的 硬化性樹脂組成物層上，以金屬膜層接觸硬化性樹脂組成 物層表面的方式，重疊層合上述（1)〜（14)中任一項 -9 - 200904283 記載的金屬膜轉印用薄膜’將硬化性樹脂組成物硬化之步 驟，剝離支持體層之步驟’及以水溶液來溶解去除金屬膜 層上所存在的脫模層之步驟。 (1 7 )如上述（1 6 )記載的方法，其中硬化性樹脂組 成物層係由使纖維所成的片狀基材含浸硬化性樹脂組成物 而成的預浸體所構成。 (1 8 )如上述（16 )或（1 7 )記載的方法，其中在以 水溶液溶解去除脫模層的步驟之後，更包含在金屬膜層上 藉由鍍敷來形成導體層之步驟。 (19) 一種覆金屬層合板之製造方法，其特徵爲在由 單一預浸體或複數片的預浸體所重疊多層化成的多層預浸 體之一面或兩面上，以金屬膜層接觸預浸體的表面之方式 ，重疊及加熱加壓上述（1 )〜（1 4 )中任一項記載的金 屬膜轉印用薄膜。 (2 0 ) —種電路基板，其係由使用上述（1 )〜（1 4 )中任一項記載的金屬膜轉印用薄膜，轉印金屬膜層所製 造。 (21) —種覆金屬層合板，其係由上述（1)〜（14 )中任一項記載的金屬膜轉印用薄膜，轉印金屬膜層所製 造。 (發明的效果） 依照本發明的金屬膜轉印用薄膜，由於具有優異的金 屬膜層轉印性，故均勻的金屬膜層轉印係成爲可能。 -10- 200904283 因此，於電路基板製造中，若使用本發明的金屬膜轉 印用薄膜，則由於不以鹼性過錳酸鉀溶液等的氧化劑將絕 緣層表面粗化，可在該表面上可形成密接性及均勻性高的 金屬膜層，故可在更溫和的條件下實施電路形成中的蝕刻 ’結果在多層印刷配線板、撓性印刷配線板等的電路基板 之微細配線化方面發揮優異的效果。 【實施方式】 (實施發明的最佳形態） 以下就較佳實施形態來詳細說明本發明。 本發明的金屬膜轉印用薄膜（以下亦僅稱爲「薄膜」 )具有：支持體層，在該支持體層上所形成的脫模層’及 在該脫模層上所形成的金屬膜層。 <支持體層> 於本發明的金屬膜轉印用薄膜中，支持體層係具有自 己支持性的薄膜或片狀物，可合適地採用塑膠薄膜。作爲 塑膠薄膜，可舉出聚對苯二甲酸乙二酯薄膜、聚萘二甲酸 乙二酯薄膜、聚醯亞胺薄膜、聚醯胺醯亞胺薄膜、聚醯胺 薄膜、聚四氟乙烯薄膜、聚碳酸酯薄膜等，較佳爲聚對苯 二甲酸乙二酯薄膜、聚萘二甲酸乙二酯薄膜，其中特佳爲 廉價的聚對苯二甲酸乙二酯薄膜。對與水溶性高分子脫模 層接觸之側的支持體薄膜表面，亦可施予聚矽氧系脫模劑 、醇酸系脫模劑、氟系脫模劑等的脫模劑之脫模處理、電 -11 - 200904283 暈處理等的表面處理。 又，對不與水溶性高分子接觸之側的支持體薄膜表面 ，亦可施予消光處理、電暈處理等的表面處理。 另外，支持體層的層厚通常爲ΙΟμιη〜70μιη，較佳爲 1 5 μιη〜7 0 μιη。層厚若太小，則操作性差，而且支持體層 的剝離性或金屬膜層的平滑性有降低的傾向。層厚若太大 ，則成本上不利而不實用。 <脫模層> 脫模層係使用由水溶性纖維素樹脂、水溶性聚酯樹脂 及水溶性丙烯酸樹脂所選出的1種以上之水溶性高分子。 其中’更佳爲水溶性纖維素樹脂或水溶性聚酯樹脂，特佳 爲水溶性纖維素樹脂。通常，於水溶性高分子脫模層中， 使用單獨的任一種水溶性高分子，也可混合2種以上的水 溶性高分子來使用。又，通常以單層來形成水溶性高分子 脫模層，但亦可具有由所使用的水溶性高分子爲互相不同 的2層以上之層所形成的多層構造。 (水溶性纖維素樹脂） 本發明中所言的「水溶性纖維素樹脂」係施有賦予纖 維素水溶性的處理之纖維素衍生物者，較佳可舉出纖維素 醚、纖維素醚酯等。 纖維素醚係指爲了在纖維素聚合物中給予1個以上的 醚連結基，由纖維素聚合物的1個以上之葡萄糖酐重複單 -12- 200904283 位中所存在的1個以上之羥基的轉換所形成的醚；於醚連 結基中，通常可舉出可經.羥基、羧基、烷氧基（碳數1〜4 )及羥基烷氧基（碳數1〜4 )所選出的1種以上之取代基 所取代的烷基（碳數1〜4)。具體地，可舉出2 -羥乙基 、2 -羥丙基、3 -羥丙基等的羥烷基（碳數1〜4) ;2 -甲氧 基乙基、3-甲氧基丙基、2-甲氧基丙基、2-乙氧基乙基等 的烷氧基（碳數1〜4)烷基（碳數1〜4) ; 2-(2-羥基乙 氧基）乙基等的2- ( 2-羥基丙氧基）丙基等的羥基烷氧基 (碳數1〜4)烷基（碳數1〜4)、羧甲基等的羧烷基（ 碳數1〜4)等。聚合物分子中的醚連結基可爲單一種或複 數種。即，可爲具有單一種的醚連結基之纖維素醚，也可 爲具有複數種的醚連結基之纖維素醚。 作爲纖維素醚的具體例子，例如可舉出甲基纖維素、 羥乙基纖維素、羥丙基纖維素、羥丙基甲基纖維素、羥丁 基甲基纖維素、羥乙基乙基纖維素、羧基甲基纖維素及此 等的水溶性鹽（例如鈉鹽等的鹼金屬鹽）。 再者’纖維素醚的每單位葡萄糖環之取代醚基的平均 莫耳數係沒有特別的限定，較佳爲1〜6。又，纖維素醚的 分子量以重量平均分子量計較佳爲20000〜60000左右。 另一方面，纖維素醚酯係指由纖維素中所存在的丨個 以上的羥基及1個以上的合適之有機酸或其反應性衍生物 之間所形成，藉此在纖維素醚中形成酯連結基的酯。再者 ，此處所言的「纖維素醚」係如上述，「有機酸」包括脂 肪族或芳香族羧酸（碳數2〜8 )，脂肪族羧酸可爲非環狀 -13- 200904283 (分枝狀或非分枝狀）或環狀，也可爲飽和或不飽和。具 體地’作爲脂肪族羧酸，例如可舉出醋酸'丙酸、丁酸、 戊酸、丙二酸、琥珀酸、戊二酸、富馬酸、馬來酸等的取 代或未取代的非環狀脂肪族二羧酸；乙醇酸或乳酸等的非 環狀脂肪族羥基取代單羧酸；蘋果酸、酒石酸、檸檬酸等 的非環狀脂肪族羥基取代二或三羧酸等。又，作爲芳香族 羧酸’較佳爲碳數14以下的芳族羧酸，特佳具有丨個以 上的羧基（例如1、2或3個羧基）之含有苯基或萘基等 的芳基之芳族羧酸。再者，芳基可經選自於羥基、碳數1 〜4的烷氧基（例如甲氧基）及磺醯基的相同或不同之1 個以上（例如1、2或3 )的基所取代。於芳族羧酸的合適 例中’可舉出苯二甲酸、異苯二甲酸、對苯二甲酸或偏苯 三酸（1,2,4-苯三羧酸）等。 於有機酸具有1個以上的羧基時，較佳爲酸的僅1個 羧基係對纖維素醚形成酯連結。例如，於羥丙基甲基纖維 素琥珀酸酯時’各琥珀酸酯基的1個羧基與纖維素形成酯 連結，其它羧基當作游離酸存在。「酯連結基」係由纖維 素或纖維素醚與前述合適的有機酸或其反應性衍生物之反 應所形成。於合適的反應性衍生物中，例如包括苯二甲酸 酐等的酸酐。 聚合物分子中的酯連結基可爲單一種或複數種。即， 可爲具有單一種的酯連結基之纖維素醚酯，也可爲具有複 數種的酯連結基之纖維素醚酯。 例如’羥丙基甲基纖維素醋酸酯琥珀酸酯係具有琥拍 -14- 200904283 酸酯基與醋酸酯基兩者的羥丙基甲基纖維素 合適的纖維素醚酯係羥丙基甲基纖維素 素的酯，具體地可舉出羥丙基甲基纖維素醋 甲基纖維素琥珀酸酯、羥丙基甲基纖維素醋 、羥丙基甲基纖維素苯二甲酸酯、羥丙基甲 三酸酯、羥丙基甲基纖維素醋酸酯苯二甲酸 基纖維素醋酸酯偏苯三酸酯、羥丙基纖維素 酸酯、羥丙基纖維素丁酸酯苯二甲酸酯、羥 酸酯苯二甲酸酯琥珀酸酯及羥丙基纖維素醋 酯琥珀酸酯等，此等可使用1種或2種以上 ，較佳爲羥丙基甲基纖維素苯二甲酸醋、經 素醋酸酯琥珀酸酯、羥丙基甲基纖維素醋酸 ΰ 再者’纖維素醚酯的每單位葡萄糖環之 均莫耳數係沒有特別的限定，較佳爲〇.5% ，纖維素醚醋的分子量以重量平均分子量言十 〜60000左右。 纖維素醚、纖維素醚酯的製法係眾所周[ 天然的纖維素（紙漿）當作原料，依照 化劑、酯化劑反應而得，但於本發明中亦可 例如，信越化學工業（股）製「HP_55」、 爲羥丙基甲基纖維素苯二甲酸醋）等。 (水溶性聚酯樹脂） t混合酯。 或羥丙基纖維 酸酯、羥丙基 酸酯琥珀酸酯 基纖維素偏苯 酯、羥丙基甲 醋酸酯苯二甲 丙基纖維素醋 酸酯偏苯三酸 。於此等之中 丙基甲基纖維 醋苯二甲酸酯 取代酯基的平 - 2 %左右。又 較佳爲20000 知，可以來自 的方法，與醚 使用市售品。 HP-50」（皆 -15- 200904283 本發明中所言的「水溶性聚酯樹脂」係指多元羧酸或 其酯形成性衍生物與多元醇或其酯形成性衍生物當作主要 原料，藉由通常的聚縮合反應所合成之實質上由線狀的聚 合物所成之聚酯樹脂，分子中或分子末端導入有親水基者 。此處，作爲親水基，磺酸基、羧基、磷酸基等的有機酸 基或其鹽等，較佳爲磺酸基或其鹽、羧基或其鹽。作爲水 溶性聚酯樹脂，特佳爲磺酸基或其鹽及/或羧基或其鹽。 作爲該聚酯樹脂的多元羧酸成分之代表例，有對苯二 甲酸、異苯二甲酸、苯二甲酸、苯二甲酸酐、2,6-萘二羧 酸、1,4-環己烷二羧酸、己二酸等，此等可單獨使用，亦 可倂用2種以上。又，與上述各種化合物一起，亦可少量 倂用如對羥基苯甲酸等的羥基羧酸、馬來酸、富馬酸或伊 康酸等般的不飽和羧酸。 作爲該聚酯樹脂的多元醇成分之代表例’有乙二醇、 1，4-丁二醇、新戊二醇、二乙二醇、二丙二醇、1，6-己二 醇、1,4 -環己烷甲醇、苯二甲基二醇、二羥甲基丙酸、甘 油、三羥甲基丙烷或聚（四亞甲基氧化物）二醇等’此等 可單獨使用，也可倂用2種以上。 對該聚酯樹脂的分子中或分子末端導入親水基係可藉 由眾所周知慣用的方法來進行’較佳爲將含有親水基的醋 形成性化合物（例如芳香族羧酸化合物、經基化合物等） 共聚合的態樣。 例如，於導入磺酸鹽基時’較佳爲共聚合從5 _磺酸納 異苯二甲酸、5_磺酸銨異苯二甲酸、4 -磺酸鈉異苯二甲酸 -16- 200904283 、4 -甲基磺酸銨異苯二甲酸、2_磺酸鈉對苯二甲酸、5-磺 酸鉀異苯二甲酸、4-磺酸鉀異苯二甲酸及2-磺酸鉀對苯二 甲酸等所選出的1或2種以上者。 又，於導入羧基時，例如較佳爲共聚合從偏苯三酸酐 、偏苯三酸、均苯四酸酐 '均苯四酸、均苯三酸、環丁烷 四羧酸、二羥甲基丙酸等所選出的1或2種以上者，於該 共聚合反應之後’藉由胺基化合物、氨或鹼金屬鹽等使中 和，可在分子中導入羧酸鹽基。 水溶性聚酯樹脂的分子量係沒有特別的限制，重量平 均分子量較佳爲10000〜40000左右。重量平均分子量若 低於1 0000，則層形成性有降低的傾向，而若超過40000 ，則溶解性有降低的傾向。 於本發明中’水溶性聚酯樹脂係可以使用市售品，例 如可舉出互應化學工業（股）製的「Plascoat Z_561」（ 重量平均分子量：約27000 ) 、「Plascoat Z-565」（重量 平均分子量：約25000 )等。 (水溶性丙烯酸樹脂） 本發明中所言的「水溶性丙烯酸樹脂」，係指含有含 Μ基的單體當作必要成分，分散或溶解在水中的丙烯酸樹 脂。 胃丙稀酸樹脂更佳係以含羧基的單體及（甲基）丙烯 作必要的單體成分，視需要含有其它不飽和單體當 作單體成分的丙烯酸系聚合物。 -17- 200904283 於上述單體成分中，作爲含羧基的單體，例如可舉出 (甲基）丙烯酸、馬來酸、富馬酸、巴豆酸、伊康酸、檸 康酸、馬來酸酐、馬來酸單甲酯、馬來酸單丁酯、伊康酸 單甲酯、伊康酸單丁酯等，可以使用此等之中的1種或2 種以上。於此等之中，較佳爲（甲基）丙烯酸。 又，作爲（甲基）丙烯酸酯，例如可舉出（甲基）丙 烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸正丙酯 、（甲基）丙烯酸正丁酯、（甲基）丙烯酸異丁酯、（甲 基）丙烯酸正戊酯、（甲基）丙烯酸正己酯、（甲基）丙 烯酸正庚酯、（甲基）丙烯酸正辛酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸壬酯、（甲基）丙烯酸癸酯、 (甲基）丙嫌酸十二酯、（甲基）丙烯酸十八酯等的烷基 之碳數爲1〜18的甲基丙烯酸烷酯’可以使用此等之中的 1種或2種以上。 又’作爲其它不飽和單體，例如可舉出芳香族烯基化 合物、丙嫌腈化合物、共軛二烯系化合物、含鹵素的不飽 和化合物、含羥基的單體等。作爲芳香族烯基化合物，例 如可舉出本乙烯、α -甲基苯乙烯、對甲基苯乙烯、對甲氧 基本乙烯等。作爲丙烯腈化合物’例如可舉出丙烯腈、甲 基丙烯腈寺。作爲共軛二烯系化合物，例如可舉出丁二烯 、異戊二烯等。 作爲含鹵素的不飽和化合物，例如可舉出氯乙烯、偏 二氯乙烯、全氟乙烯、全氟丙烯、偏二氟乙烯等。作爲含 羥基的單體，例如可舉出（甲基）丙烯酸酯2_羥乙酯、（ -18- 200904283 甲基）丙烯酸2-羥丙酯、（甲基）丙烯酸3-羥丙酯 基）丙烯酸2-羥丁酯、4-羥丁基丙烯酸酯、甲基丙 羥丁酯、（甲基）丙烯酸α-羥基甲基乙酯等。此等 1種或2種以上。 如後述地，於本發明中，脫模層較佳係藉由將 性纖維素樹脂、水溶性聚酯樹脂或水溶性丙烯酸樹 佈液塗佈在支持體上及進行乾燥的方法來形成。於 溶性丙烯酸樹脂時，該塗佈液可使用乳液形態，也 水溶液形態。 於以乳液形態使用水溶性丙烯酸樹脂時，較佳 型乳液；於芯殼型乳液中，在芯殻粒子的殼中有羧 在係重要，因此，殼係由含有含羧基的單體及（甲 烯酸酯的丙烯酸樹脂所構成。 如此的芯殼粒子之分散品（乳液）係可使用市 例如可舉出 Joncryl 7600 ( Tg :約 35°C ) 、7630Α 約 53°C ) 、5 3 8J ( Tg :約 66°C ) 、3 52D ( Tg :約 (皆爲BASF日本公司（股）製）等。 於以水溶液形態使用水溶性丙烯酸樹脂時，該 樹脂係含有含羧基的單體及（甲基）丙烯酸酯之丙 脂’比較低的分子量係重要。因此，重量平均分子 爲1000〜50000，重量平均分子量若低於1000，則 性有降低的傾向，而重量平均分子量若超過5 0000 支持體的密接性變高，硬化後的支持體之剝離性有 傾向。 、（甲 缔酸4- 可使用 含水溶 脂的塗 使用水 可使用 爲芯殻 基的存 基）丙 售品， (Tg ： 5 6〇C ) 丙烯酸 烯酸樹 量較佳 層形成 ，則與 降低的 -19- 200904283 如此的水溶性丙烯酸樹脂之水溶液係可使用市售品， 例如可舉出J〇ncryl 354J(BASF日本公司（股）製）等。 再者，於水溶性丙烯酸樹脂的乳液及水溶液中，乳液 由於分子量高而容易薄膜化。因此，較佳爲水溶性丙烯酸 樹脂的乳液。 於本發明中，在支持體層上形成脫模層的方法係沒有 特別的限定，可以採用熱壓機、熱輥層合機、擠出層合機 、塗佈液的塗佈·乾燥等眾所周知的層合方法，但從簡便 、可容易形成性質狀態均勻性高的層等之點來看，較佳爲 塗佈含水溶性纖維素、水溶性聚酯或水溶性丙烯酸樹脂的 塗佈液及進行乾燥的方法。 於本發明中，脫模層可爲單層或多層（積層）。即， 可由從水溶性纖維素層、水溶性聚酯樹脂層及水溶性丙烯 酸樹脂層所選出的至少1層所構成，也可由2層以上的多 層（層合層）所構成。 脫模層的層厚通常爲Ο.ίμιη〜20μπι，較佳爲0.2μιη〜 ΙΟμιη，更佳爲0.2〜5μιη。此處所言的「層厚」，於脫模 層爲單層時係指其厚度，於多層時係指多層的總厚度。層 厚若太薄’則支持體層的剝離性有降低之虞，而層厚若太 厚，則在將硬化性樹脂組成物層熱硬化時，則由於金屬膜 層與脫模層的熱膨脹率不同，金屬膜層會有發生裂紋或傷 痕等的不良情況之虞。 <金屬膜層> -20- 200904283 作爲金屬膜層，可使用金、舶、銀、銅、鈷、鉻、鎳 、鈦、鎢、鐵、錫、銦等的金屬單體，以及適宜地2種類 以上的金屬之固溶體（合金）等所有種類的金屬，其中從 成本、蒸鍍法或濺鍍法的通用性、導電性之點來看，較佳 爲鉻、鎳、鈦、鎳-鉻合金、鋁、金、銀及銅，於電路基 板的配線用時，特佳爲銅。 又’金屬膜層可由單層或不同金屬的2層以上之層合 層所構成。例如，於採用該薄膜製造電路基板時，將銅層 層合在基板上的樹脂組成物層表面或預浸體表面上，對該 樹脂組成物層或預浸體進行熱硬化的步驟中，若爲擔心由 於銅對樹脂組成物或預浸體的擴散而使樹脂產生熱降解（ 分解）等的系統，則按照需要，可在銅層上設置鉻層、 鎳-鉻合金層或鈦層。即’於水溶性高分子脫模層上形成 銅層後，更可形成絡層、鎳-鉻層或鈦層。 從膜性能之點及與硬化性樹脂組成物層的密接之觀點 來看’金屬膜層的形成方法較佳係藉由濺鍍法或/及蒸鍍 法來形成。 金屬膜層的層厚係沒有特別的限制，通常爲5 〇ηιη〜 5000nm，較佳爲 50nm 〜30〇〇nm，更佳爲 100nm〜 3000nm ，特佳爲lOOnm〜lOOOnm。層厚若太小，則於電路基板的 製造中，由於電解鍍敷操作中的損傷等，在金屬膜層上產 生不均’導體層的形成有發生不良情況之虞。另一方面， 層厚若太大，則以潤鍍法或/及蒸鍍法來形成金屬膜時需 要長時間’從成本的觀點係不宜。再者，於成爲如上述的 -21 - 200904283 銅層/鉻層、鎳-鉻合金層或鈦層的2層構造時’全體的層 厚係與上述相同，而且鉻層、鎳-鉻層或鈦層的厚度較佳 爲5nm〜100nm，更佳爲5nm〜50nm’特佳爲5nm〜30nm ，最佳爲5〜20nm。 本發明的金屬膜轉印用薄膜在金屬膜層的轉印’係至 少藉由在表層由硬化性樹脂組成物所成的被附體（被轉印 體）上，以金屬膜層接觸被附體（被轉印體）的表面之方 式，重疊層合（層壓）該薄膜，於此狀態下使硬化性樹脂 組成物硬化後，剝離支持體層，以水溶液來溶解去除金屬 膜層上所存在的脫模層而進行。 即，藉由硬化性樹脂組成物的硬化而使金屬膜層強固 地黏著於被附體（被轉印體），另一方面，於支持體層的 剝離後，雖然剝離層殘留在金屬膜層上，但由於以水溶液 來溶解去除由水溶性纖維素層、水溶性聚酯樹脂層或水溶 性丙烯酸樹脂層所構成的脫模層，而在硬化性樹脂組成物 所成的被附體與金屬膜層之間不會發生起泡，金屬膜層不 會發生的皺紋、龜裂等，金屬膜層可均勻轉印。再者，於 硬化處理前剝離時，金屬膜層係無法充分轉印，於硬化性 樹脂組成物的硬化後，金屬膜層會容易發生龜裂等的不良 情況。 上述硬化性樹脂組成物係沒有特別的限定，可使用於 環氧樹脂、氰酸酯樹脂、苯酚樹脂、雙馬來醯亞胺-三Π并樹 脂、聚酿亞胺樹脂、丙嫌酸樹脂、乙烯基苄基樹脂等的可 硬化之基礎樹脂中，至少摻有該樹脂的一般硬化劑之樹脂 -22- 200904283 組成物。又，亦可更摻合硬化促進劑。 該薄膜對被附體的層合，從作業性及容易得到一樣的 接觸狀態之點來看，較佳爲藉由輥或加壓機來壓黏等，以 將薄膜層壓（laminate )在被附體表面上的處理。其中， 較佳爲藉由真空層壓法，在減壓下進行層壓。又，層壓的 方法可爲分批式，也可爲用輥的連續式。 層壓的條件一般較佳爲以壓黏壓力在1〜1 lkgf/cm2 ( 9·8χ104 〜107·9χ104 N/m2)的範圍，空氣壓在 20mmHg( 26.7hPa)以下的減壓下，進行層壓。 真空層壓係可使用市售的真空層壓機。作爲市售的真 空層壓機，例如可舉出（股）名機製作所製分批式真空加 壓層壓機 MVLP-5 00，Nichigo-Morton (股）製 Vacuum Applicator > (股）日立工業製滾筒式乾塗佈機，曰立 AIC (股）製真空層壓機等。 於本發明中，作爲在剝離支持體層後，用於溶解去除 金屬膜層上的脫模層之水溶液，可舉出使碳酸鈉、碳酸氫 鈉、氫氧化鈉、氫氧化鉀等以0 · 5〜1 0重量％的濃度溶解 在水中的鹼性水溶液等。通常，無以下的必要，但爲了在 電路基板等的製造上沒有問題的範圍內，亦可在水溶 '液φ 含有甲醇、乙醇、異丙醇等的醇。溶解去除的方法係沒有 特別的限定，例如可舉出於剝離支持體層後，將基板丨曼胃 在水溶液中以溶解去除的方法，將水溶液以噴霧狀或霧狀 噴塗以溶解去除的方法等。水溶液的溫度通常爲室溫~ 8(TC左右，浸水、噴塗等的處理時間通常可進行10秒 -23- 200904283 1 0分鐘。作爲驗性水溶液，亦可使用電路基板製造時所使 用的鹼顯像機之驗型顯像液（例如〇 . 5〜2重量％的碳酸鈉 水溶液’ 25°C〜40°C )、乾膜剝離機之剝離液（例如1〜5 重量％的氫氧化鈉水溶液，4 0。<3〜6 0 °C )、去膠澄（ desmear )步驟所使用的膨潤液（例如含有碳酸鈉、氫氧 化鈉等的鹼水溶液，6 0 °C〜8 0 °C )等。 本發明的金屬膜轉印用薄膜的金屬膜層所轉印的被附 體（被轉印體），只要至少其表面層由硬化性樹脂組成物 所構成即可，並沒有特別的限制。 本發明的金屬膜轉印用薄膜，特別適合在撓性配線板 、多層印刷配線板等的電路基板的製造步驟中，用於導體 層的形成。 製造使用本發明的金屬膜轉印用薄膜之電路基板的方 法係經由以下（A )〜（C )的步驟之方法。 (A )於基板上所形成的硬化性樹脂組成物層上，以 金屬膜層接觸硬化性樹脂組成物層表面的方式，重疊層合 本發明的金屬膜轉印用薄膜，將硬化性樹脂組成物層硬化 °藉此，使金屬膜轉印用薄膜的金屬膜層與硬化性樹脂組 成物層黏著。 (B )其次，剝離金屬膜轉印用薄膜的支持體層。支 持體層的剝離可由手動來剝離，也可藉由自動剝離裝置來 機械地剝離。 (C )接著，以水溶液來溶解去除剝離支持體層後的 金屬膜層上所存在的脫模層。 -24- 200904283 經過上述（A )〜（C )的步驟後，將所轉印的金屬膜 層照原樣地當作導體層（配線層），或是（D )於所轉印 的金屬膜層上，藉由鍍敷（無電解鍍敷及/或電解鍍敷） ，以更使金屬層成長而形成導體層（配線層）。鍍敷所成 的金屬層，通常係與金屬膜層相同的金屬種類，但亦可形 成不同金屬種類的金屬層。作爲合適的一例，例如可舉出 金屬膜層爲銅層，或是在銅層上形成有鉻層或鎳-鉻合金 層的層合層時，轉印後在表層的銅層上形成鍍銅層的態樣 。於本發明中，鍍層的厚度雖然亦取決於金屬膜層的厚度 、所欲的電路基板之設計，但一般爲3〜35μιη，較佳爲5 〜3 0 μηι 〇 本發明所言的「基板」係指玻璃環氧樹脂基板、金屬 基板、聚酯基板、聚醯亞胺基板、ΒΤ樹脂基板、熱硬化 型聚苯醚基板等，或於此等基板的一面或兩面上具有經圖 型加工（形成電路）的導體層，於製造電路基板時，更包 含成爲適用於形成絕緣層及導體層之中間製造物的所謂「 內層電路基板」之槪。又，本發明所言的「電路基板」只 要具有絕緣層及形成電路的導體層即可，並沒有特別的限 定，可舉出多層印刷配線板、撓性印刷配線板等的各種電 路基板。 於本發明中，作爲形成在基板上的硬化性樹脂組成物 層所使用的硬化性樹脂組成物，可採用以往在多層印刷配 線板等的電路基板中作爲絕緣層所使用之眾所周知的硬化 性樹脂組成物，並沒有特別的限制，例如可使用於環氧樹 -25 - 200904283 脂、氰酸酯樹脂、苯酚樹脂 '雙馬來醯亞胺-三畊樹脂、聚 醯亞胺樹脂、丙烯酸樹脂、乙烯基苄基樹脂等的硬化性樹 脂中至少摻有其硬化劑的組成物。從與金屬膜層的密著性 、絕緣可靠性之點來看，較佳爲至少含有（a)環氧樹脂 、（b)熱塑性樹脂及（c )硬化劑的組成物。 作爲（a)環氧樹脂，例如可舉出雙酚a型環氧樹脂 、聯苯型環氧樹脂、萘酚型環氧樹脂、萘型環氧樹脂、雙 酚F型環氧樹脂、含磷的環氧樹脂、雙酚s型環氧樹脂、 脂環式環氧樹脂、脂肪族鎖狀環氧樹脂、苯酚酚醛清漆型 環氧樹脂 '甲酚酚醛清漆型環氧樹脂、雙酚A酚醛清漆型 環氧樹脂、具有丁二烯構造的環氧樹脂、雙酚的二縮水甘 油醚化物、萘二醇的二縮水甘油醚化物、酚類的縮水甘油 醚化物、及醇類的二縮水甘油醚化物、以及此等環氧樹脂 的烷基取代物、鹵化物及氫化物等。此等環氧樹脂可使用 任一種，也可混合2種以上來使用。 於此等之中，從耐熱性、絕緣可靠性、與金屬膜的密 接性之觀點，環氧樹脂較佳爲雙酚A型環氧樹脂、萘型環 氧樹脂、萘酚型環氧樹脂、具有丁二烯構造的環氧樹脂、 聯苯型環氧樹脂等。具體地，例如可舉出液狀雙酚A型環 氧樹脂（日本環氧樹脂（股）製「Epicoat 82 8EL」）、萘 型2官能環氧樹脂（大日本油墨化學工業（股）製「 HP4032」、「HP4032D〕）、萘型4官能環氧樹脂（大日 本油墨化學工業（股）製「HP4700」）、萘酚型環氧樹脂 (東都化成（股）製「ESN-4 7 5V」）、具有丁二烯構造 -26- 200904283 的環氧樹脂（DAICEL化學工業（股）製「PB-3600 j )、 聯苯型多官能環氧樹脂（日本化藥（股）製「NC3 000H」 、「NC3000L」）、）、聯苯型環氧樹脂（日本環氧樹脂 (股）製「YX4000」）等。 (b )熱可塑性樹脂係以賦予硬化後的組成物適度的 可撓性等爲目的而配合者，例如苯氧樹脂、聚乙烯縮醛樹 脂、聚醯亞胺、聚醯胺醯亞胺、聚醚颯、聚颯等。此等可 單獨使用任1種類，也可倂用2種以上。以硬化性樹脂組 成物的不揮發成分爲1 〇 〇質量％時，該熱塑性樹脂較佳爲 以0.5〜60質量％的比例來配合，更佳爲3〜50質量％。熱 塑性樹脂的配合比例若低於〇 . 5質量％，則由於樹脂組成 物的黏度低，於塗佈乾燥時，有難以形成均勻的硬化性樹 脂組成物層之傾向，而若超過60質量％，則樹脂組成物的 熔融黏度高，對基板上的配線圖型之埋入會有變困難的傾 向。 作爲苯氧樹脂的具體例，例如可舉出東都化成（股） 製 FX280、FX293、日本環氧樹脂（股）製 YX8100、 YL6954 、 YL6974 等。 聚乙烯縮醛樹脂較佳爲聚乙烯縮丁醛樹脂，作爲聚乙 烯縮醛樹脂的具體例’可舉出電氣化學工業（股）製的電 化縮丁醛 4000-2、 5000-A、 6000-C、 6000-EP，積水化學 工業（股）製S-LEC BH系列、BX系列、KS系列、BL系 列、BM系列等。 作爲聚醯亞胺的具體例，可舉出新日本理化（股）製 -27- 200904283 的聚醯亞胺「Rikacoat SN20」及「Rikacoat PN20」。又 ，可舉出使2官能性羥基末端聚丁二烯、二異氰酸酯化合 物及四元酸酐反應而得之線狀聚醯亞胺（特開2006-3 7083 號公報中記載者）、含有聚矽氧烷骨架的聚醯亞胺（特開 2002- 1 2667號公報，特開2 000-3 1 93 86號公報等中記載者 )等的改性聚醯亞胺。 作爲聚醯胺醯亞胺的具體例，可舉出東洋紡績（股） 製的聚醯胺醯亞胺「Vylomax HR11NN」及「Vylomax HR16NN」，日立化成工業（股）製的含有聚矽氧烷骨架 的聚醯胺醯亞胺「KS9100」、「KS9300」等。 作爲聚醚颯的具體例，可舉出住友化學（股）製的聚 醚砸「PES 5 003 P」等。 作爲聚楓的具體例，可舉出 Solvay Advanced Polymers (股）製的聚颯「P1700」、「P3500」等。 作爲（c )硬化劑，例如可舉出胺系硬化劑、胍系硬 化劑、咪唑系硬化劑、酚系硬化劑、萘酚系硬化劑、酸酐 系硬化劑或此等的環氧加成物或微膠囊化者、氰酸酯樹脂 等。其中，較佳爲酚系硬化劑、萘酚系硬化劑、氰酸酯樹 脂。再者，於本發明中，硬化劑係可爲1種或倂用2種以 上。 作爲酚系硬化劑、萘酚系硬化劑的具體例，例如可舉 出 MEH-7700、MEH-78 10、MEH-785 1 (明和化成（股） 製）、NHN、CBN、GPH (日本化藥（股）製）、SN170 、SN180、SN190、SN475、 SN48 5、SN495、SN 3 7 5、 -28- 200904283 SN3 95 (東都化成（股）製）、LA7052、LA7054、 LA 3018、LA1356(大日本油墨化學工業（股）製）等。 作爲氰酸酯樹脂的具體例，例如可舉出雙酚A二氰酸 酯、聚酚氰酸酯（寡聚（3-亞甲基-1，5-伸苯基氰酸酯）） 、4，4’-亞甲基雙（2,6-二甲基苯基氰酸酯）、4,4，-亞乙基 二苯基二氰酸酯、六氟雙酚A二氰酸酯、2,2-雙（4-氰酸 酯）苯基丙烷、1，1-雙（4-氰酸酯苯基甲烷）、雙（4_氰 酸酯-3,5-二甲基苯基）甲烷、1，3-雙（4-氰酸酯苯基_丨-( 甲基亞乙基））苯、雙（4-氰酸酯苯基）硫醚、雙（4-氰 酸酯苯基）醚等的2官能氰酸酯樹脂、酚酚醛清漆、甲酚 酚醛清漆等所衍生的多官能氰酸酯樹脂、此等氰酸酯樹脂 的一部分經三Π并化的預聚物等。作爲市售的氰酸酯樹脂， 可舉出苯酚酚醛清漆型多官能氰酸酯樹脂（LONZA日本 (股）製，PT3 0,氰酸酯當量124)或雙酚A二氰酸酯的 一部分或全部經三阱化的三聚物之預聚物（LONZA日本（ 股）製，BA230，氰酸酯當量232)等。 (a )環氧樹脂與（c )硬化劑的配合比率，於酚系硬 化劑或萘酚系硬化劑時，對於環氧樹脂的1環氧當量而言 ’此等硬化劑的酚性羥基當量較佳爲在0 · 4〜2.0的範圍內 之比率，更佳爲在0.5〜1.0的範圍內之比率。於氰酸酯樹 脂時，對於1環氧當量而言，氰酸酯當量較佳爲在〇.3〜 3.3的範圍內之比率，更佳爲在〇.5〜2.0的範圍內之比率 。反應基當量比若在該範圍外，則硬化物的機械強度或耐 水性有降低的傾向。 -29- 200904283 再者，於當該硬化性樹脂組成物中’除了（c)硬化 劑，亦可更摻合（d )硬化促進劑。作爲如此的硬化促進 劑，可舉出咪唑系化合物、有機膦系化合物等，作爲具體 例，例如可舉出2 -甲基咪唑、三苯基膦等。 於使用（d )硬化促進劑時，對於環氧樹脂而言，較 佳爲以0 _ 1〜3.0質量°/。的範圍來使用。再者，於環氧樹脂 硬化劑中使用氰酸酯樹脂時，以縮短硬化時間爲目的，亦 可添加以往在倂用環氧樹脂組成物與氰酸酯化合物的系統 中當作硬化觸媒所使用的有機金屬化合物。作爲有機金屬 化合物，乙醯丙酮化銅（II )等的有機銅化合物、乙醯丙 酮化鋅（II )等的有機鋅化合物、乙醯丙酮化鈷（II )、 乙醯丙酮化鈷（III )等的有機鈷化合物等。有機金屬化合 物的添加量，對於氰酸酯樹脂而言，以金屬換算通常爲10 〜500PPm，較佳爲在25〜200Ppm的範圍。 又，於該硬化性樹脂組成物中，爲了硬化後組成物的 低熱膨脹化，可含有（e )無機塡充劑。作爲無機塡充劑 ’例如可舉出矽石、氧化鋁、雲母、雲母（m i c a )、矽酸 鹽、硫酸鋇、氫氧化鎂 '氧化鈦等，較佳爲矽石、氧化鋁 ’特佳爲矽石。再者’從絕緣可靠性的觀點來看，無機塡 充劑的平均粒徑較佳爲3 μπι以下，平均粒徑更佳爲丨.5 μηι 以下。硬化性樹脂組成物中的無機塡充劑之含量，以硬化 性樹脂組成物的不揮發成分爲1 0 〇質量％時，較佳爲2 0〜 6 〇質量°/〇，更佳爲2 0〜5 0質量％。無機塡充劑的含量若低 於20重量％ ’則熱膨脹率的降低效果有不能充分發揮的傾 -30- 200904283 向，無 強度有 於 作爲其 的磷化 等的難 、歐本 矽氧系 唑系、 藍、酞 於 厚度亦 ，從層 右，更 硬 條件亦 爲 120 比較低 升邊使 係較宜 於 化性樹 爲藉由 佈液（ 機塡充劑的含量若超過6 〇重量％，則硬化物的機械 降低等的傾向。 該硬化性樹脂組成物中，視需要可摻合其它成分。 它成分，例如可舉出有機磷系難燃劑、有機系含氮 合物、氮化合物、聚矽氧系難燃劑、金屬氫氧化物 燃劑、聚矽氧粉末、耐隆粉末、氟粉末等的塡充劑 (Orben)、氯化聚醚（Pent〇n)等的增黏劑、聚 、氟系、局分子系的消泡劑或均平劑、咪唑系、噻 三嗤系、砂院系偶合劑等的密接性賦予劑、酞花青 花青綠、碘綠、二重氮黃、碳黑等的著色劑等。 本發明中’基板上所形成的硬化性樹脂組成物層之 隨著內層電路導體層厚而不同，但沒有特別的限定 間的絕緣可靠性等觀點來看，較佳爲1 〇〜1 5 0 μπι左 佳爲15〜80μηι。 化性樹脂組成物的硬化處理通常爲熱硬化處理，其 隨著硬化性樹脂的種類等而不同，但硬化溫度一般 〜200 °C，硬化時間一般爲15〜90分鐘。再者，從 的硬化溫度往高的硬化溫度使階段地硬化，或邊上 硬化，從所形成的絕緣層表面之皺紋防止觀點來看 〇 本發明的電路基板之製造方法中，在基板上形成硬 脂組成物層的形成方法係沒有特別的限定，但較佳 調製由硬化性樹脂組成物的溶液或分散液所成的塗 清漆），將該塗佈液（清漆）塗佈在支持薄膜上’ -31 - 200904283 進行乾燥，製作擔持有硬化性樹脂組成物層的黏著薄膜， 將該黏著薄膜的硬化性樹脂組成物層層壓於基板的一面或 兩面，剝離支持薄膜而形成。層壓較佳爲藉由真空層壓法 在減壓下進行層壓。又，層壓方法可爲分批式，也可爲用 輥的連續式。層壓條件較佳係以壓黏壓力爲在 1〜 llkgf/cm2 ( 9.8χ104 〜107.9χ104)的範圍，空氣壓爲 20mmHg ( 26.7hPa )以下的減壓下，進行層壓。再者，真 空層壓係可使用市售的真空層壓機來進行、具體例係如前 述。 作爲黏著薄膜的支持薄膜，可舉出聚乙烯、聚丙烯、 聚氯乙烯等的聚烯烴、聚對苯二甲酸乙二酯、聚萘二甲酸 乙二酯等的聚酯、聚碳酸酯、聚醯亞胺等的塑膠薄膜，以 及脫模紙或銅箔、鋁箔等的金屬箔等。再者，對支持薄膜 ，除了消光處理、電暈處理，亦可施予脫模處理。 於本發明中，亦可變爲在如上述的基板上形成硬化性 樹脂組成物層的態樣，使用預浸體。本發明中的「預浸體 」係指藉由熱熔法或溶劑法，使由織維所成的片狀補強基 材含浸上述硬化性樹脂組成物，藉由加熱使半硬化者。作 爲片狀補強基材的纖維，例如可使用玻璃布或芳醯胺纖維 等當作預浸體用纖維所常用者。 熱熔法係不將樹脂溶解在有機溶劑中，而一旦將樹脂 塗佈在與樹脂之剝離性良好的塗佈紙上，則將其層壓在片 狀補強基材上，或藉由口模式塗佈機來直接塗佈等，以製 造預浸體的方法。又，溶劑法係與黏著薄膜同樣，以在有 -32- 200904283 機溶劑中溶解有樹脂的樹脂清漆含浸片狀補強基材，使片 狀補強基材含浸樹脂清漆，然後使乾燥的方法。 於本發明中，當使用預浸體來製造電路基板時，若在 重疊單一的預浸體或複數片的預浸體而多層化的多層預浸 體上，或在藉由真空層壓法將此等層壓於基板上而成的層 合體之一面或兩面的表面層之預浸體上，以金屬膜層接觸 預浸體表面的方式，重疊層合金屬膜轉印用薄膜，藉由加 熱加壓以進行預浸體的硬化，則金屬膜轉印用薄膜的金屬 膜層與預浸體會黏著。然後，剝離金屬膜轉印用薄膜的支 持體層，以水溶液來溶解去除剝離支持體層後的金屬膜層 上所存在的脫模層，將金屬膜層轉印到預浸體。又，重疊 單一的預浸體或複數的預浸體，再於其上以金屬膜層接觸 預浸體表面的方式，重疊金屬膜轉印用薄膜，藉由真空熱 壓機對配線進行埋入及硬化，如上述地，剝離金屬膜轉印 用薄膜的支持體層，去除脫模層，亦可使金屬膜層轉印到 預浸體上。又，同樣地，於重疊單一的預浸體或複數片的 預浸體而多層化的多層預浸體之一面或兩面上，以金屬膜 層接觸預浸體的表面之方式，重疊層合金屬膜轉印用薄膜 ，藉由加熱加壓來進行預浸體的硬化，亦可製造覆金屬層 合板。 預浸體的硬化處理條件、水溶性纖維素層的水溶液之 溶解去除條件、作業等係沿襲前述內容。使用真空熱壓機 時，條件一般較佳爲以壓黏壓力在 5〜20kgf/cm2 ( 49·〇χ1〇4 〜196.1xl04N/m2)的範圍，空氣壓在 20mmHg( -33- 200904283 26.7hPa )以下的減壓下，從防止絕緣層表面上所形成的 金屬膜之雛紋的觀點來看，硬化較佳爲邊從室溫上升到高 溫，邊使硬化者。 於形成電路基板時，視需要可對基板上所形成的絕緣 層進行冲孔以形成通孔（via hole)、貫穿孔（through hole )。冲孔步驟亦可在硬化處理後從支持體上進行，而 且亦可在剝離支持體後，從脫模層上進行，也可在去除脫 模層後’從金屬膜上進行。冲孔例如係可藉由鑽頭 '雷射 、電漿等眾所周知的方法，且視需要可組合此等方法來進 行，以二氧化碳雷射、Y A G雷射等的雷射來冲孔係最普通 的方法。冲孔步驟後，藉由去膠渣步驟來去除通孔底部等 所存在的膠渣。去膠渣步驟係可藉由電漿等的乾法、鹼性 過錳酸溶液等的氧化劑處理之濕法等眾所周知的方法。 於形成電路基板時，導體層（配線層）的形成係將金 屬膜層照原樣地當作導體層，或在金屬膜層上藉由無電解 鍍敷及/或電解鍍敷以更使金屬層成長而形成導體層。電 解鍍敷的金屬層，通常係與金屬膜層相同的金屬種類之金 屬層，但亦可形成不同金屬種類的金屬層。作爲合適的一 例，例如可舉出金屬膜層爲銅層，或是在銅層上形成有鉻 層或鎳-鉻合金層的層合層時，轉印後在表層的銅層上形 成鍍銅層的態樣。於本發明中，電解鍍敷層的厚度雖然亦 取決於金屬膜層的厚度 '所欲的電路基板之設計，但一般 爲3〜35μιη，較佳爲5〜30μιη。再者’於進行冲孔步驟時 ，藉由無電解鍍敷與電解鍍敷的組合或直接電鍍等眾所周 -34- 200904283 知的方法，可在孔內形成導體層。 以下，呈現實施例以更具體說明本發明，惟本發明完 全不受以下的實施例所限定。再者，於以下的記載中，「 份」係指「重量份」。 〔實施例1〕 <金屬膜轉印用薄膜的製作> 於厚度38μπι的聚對苯二甲酸乙二酯（以下簡稱PET )薄膜上’藉由口模式塗佈機來塗佈羥丙基甲基纖維素苯 二甲酸酯（信越化學工業（股）製「HP— 55」）的固體成 分10 %之甲基乙基酮（以下簡稱MEK)與N，N -二甲基甲 醯胺（以下簡稱DMF )的1 : 1溶液，使用熱風乾燥爐從 室溫以3 °C /秒的升溫速度升溫到1 40 t爲止以去除溶劑， 在PET薄膜上形成Ιμηι的羥丙基甲基纖維素苯二甲酸酯 層。接著，於經丙基纖維素苯二甲酸酯層上藉由雜鍍（Ε -400S，Canon-Anelva (股）製）來形成500nm的銅層，再 於該銅層上形成20nm的鉻層，以製作520nm的金屬膜層 之金屬膜轉印用薄膜。 <黏著薄膜的製作> 於15份的MEK與15份的環己酮之混合液中，邊攪 拌邊加熱溶解28份的液狀雙酚A型環氧樹脂（環氧當量 180，日本環氧樹脂（股）製「Epicoat 828EL」）及28份 的萘型4官能環氧樹脂（環氧當量163，大日本油墨化學 -35- 200904283 工業（股）製「HP4700」）。於其中混合110份的萘酚系 硬化劑（羥基當量215，東都化成（股）製「SN-485」） 的固體成分50%之MEK溶液、〇.1份的硬化觸媒（四國化 成工業（股）製，「2E4MZ」）' 70份的球形矽石（平均 粒徑 0.5μπι,(股）ADMATECHS 製「SOC2」）、30 份 的聚乙烯縮丁醛樹脂（積水化學工業（股）製「KS-1」） 的固體成分15 %之乙醇與甲苯的1:1溶液’在高速旋轉 的混合機中均勻分散，製作樹脂清漆。於厚度38μιη的 PET薄膜上，藉由口模式塗佈機塗佈上述清漆，使用熱風 乾燥爐來去除溶劑，製作硬化性樹脂組成物層的厚度爲 4 0 μ m的黏著薄膜。 <藉由黏著薄膜在電路基板上形成硬化性樹脂組成物層> 於以18μιη厚的銅層形成電路的玻璃環氧樹脂基板之 銅層上，用 CZ8 100 (含有唑類的銅錯合物、有機酸的表 面處理劑（MEC (股）製））來處理而施予粗化，以與銅 電路表面接觸的方式，使用分批式真空加壓層壓機MVLP- 5 00 ((股）名機製作所製商品名），將上述黏著薄膜層 壓於電路基板的兩面。層壓係減壓30秒，在13hPa以下 的氣壓進行。接著’冷卻到室溫後，剝離黏著薄膜的支持 體層’在電路基板的兩面上形成硬化性樹脂組成物層。 <藉由金屬膜轉印用薄膜來轉印金屬膜> 以金屬膜層接觸上述硬化性樹脂組成物層的方式，將 -36- 200904283 上述金屬膜轉印用薄膜層壓合於電路基板。層合係藉由使 用分批式真空加壓層壓機MVLP- 5 0 0 ((股）名機製作所 製商品名），層壓於電路基板的兩面上而進行。層壓係減 壓30秒，使氣壓成爲13hPa以下，然後藉由30秒、 7.54kgf/cm2的壓力下進行加壓而進行。之後，將硬化性 樹脂組成物層在1 5 0 °C硬化3 0分鐘，再於1 8 0 °C硬化3 0分 鐘，以形成絕緣層（硬化物層）。由該絕緣層剝離金屬膜 轉印用薄膜的支持體層即PET薄膜。剝離性係良好地以手 能容易剝離。然後，以1 %碳酸鈉水溶液來溶解去除羥丙 基甲基纖維素苯二甲酸酯層。金屬膜層係被均勻轉印’沒 有見到樹脂與金屬層間的起泡、金屬層的皺紋、金屬層的 龜裂等異常。 <鍍銅層形成> 於金屬膜層上進行電（電解）鍍銅’形成約SOgm厚 的鍍銅層，以製作多層印刷配線板。 [實施例2] <黏著薄膜的製作> 於15份的MEK與15份的環己酮之混合液中’邊攪 拌邊加熱溶解28份的液狀雙酚A型環氧樹脂（ 828EL) 及28份的萘型4官能環氧樹脂（HP-4700)。於其中混合 5 0份的酚系硬化劑即含三阱構造的酚醛清漆樹脂（固形物 的酚性羥基當量1 2 0,大曰本油墨化學工業（股）製「 -37- 200904283 LA7052」，固體成分60%的MEK溶液）、20份的苯氧樹 脂（分子量 50000,日本環氧樹脂（股）製「E1256」的 固體成分40%之MEK溶液）、0.1份的硬化觸媒（2E4MZ )、55份的球形矽石（SOC2 ) 、30份的實施例1所記載 的聚乙烯縮丁醛樹脂溶液、3份的具有丁二烯構造的環氧 樹脂（分子量27000，DAICEL化學工業（股）製「PB-3600」），在高速旋轉混合機中均勻分散，以製作樹脂清 漆。於厚度38μιη的PET薄膜上，藉由口模式塗佈機來塗 佈上述清漆，使用熱風乾燥爐來去除溶劑，製作硬化性樹 脂組成物層的厚度爲40 μηι的黏著薄膜。 <藉由黏著薄膜在電路基板上形成硬化性樹脂組成物層> 於以1 8 μηι厚的銅層形成電路的玻璃環氧樹脂基板之 銅層上，用 CZ8 100 (含有唑類的銅錯合物、有機酸的表 面處理劑（MEC (股）製））來處理而施予粗化，以與銅 電路表面接觸的方式，使用分批式真空加壓層壓機M VLP-5 00 ((股）名機製作所製商品名），將絕緣性黏著樹脂 薄膜層壓於電路基板的兩面。層壓係減壓3 0秒，在1 3hPa 以下的氣壓進行。接著，冷卻到室溫後，剝離黏著薄膜的 支持體層，在電路基板的兩面上形成硬化性樹脂組成物層 <藉由金屬膜轉印用薄膜來轉印金屬膜轉印> 以金屬膜層接觸絕緣性黏著樹脂層的方式，層合實施 -38- 200904283 例1所作成的金屬膜轉印用薄膜。層合係藉由使用分批式 真空加壓層壓機MVLP-5 00 ((股）名機製作所製商品名 )，層壓於電路基板的兩面上而進行。層壓係減壓30秒 ，使氣壓成爲13hPa以下，然後藉由30秒、7.54kgf/cm2 的壓力下進行加壓而進行。之後，將硬化性樹脂組成物層 在1 5 0 °C硬化3 0分鐘，再於1 8 0 °C硬化3 0分鐘，以形成絕 緣層（硬化物層）。由該絕緣層剝離支持體層即PET。剝 離性係良好地以手能容易剝離。然後，以1 %碳酸鈉水溶 液來溶解去除羥丙基甲基纖維素苯二甲酸酯層。金屬膜層 係被均勻轉印，沒有見到樹脂與金屬層間的起泡、金屬層 的皴紋、金屬層的龜裂等異常。 <鍍銅層形成> 於金屬膜層上進行電（電解）鍍銅，形成約3 Ομηι厚 的鍍銅層，以製作多層印刷配線板。 [實施例3 ] <黏著薄膜的製作> 混合3 0份的雙酚Α二氰酸酯的預聚物（氰酸酯當量 23 2，LONZA日本（股）製「BA23 0S75」，固體成分75% 的MEK溶液）、10份的苯酚酚醛清漆型多官能氰酸酯樹 脂（氰酸酯當量124, LONZA日本（股）製「PT30」）、 4〇份的萘酚型環氧樹脂（環氧當量3 40,東都化成（股） 製「ESN-475V」）的固體成分65%之MEK溶液、5份的 -39- 200904283 液狀雙酚A型環氧樹脂（8 2 8 EL ) 、1 5份的苯氧樹脂溶液 (東都化成（股）製「YP-70」，固體成分40%的MEK與 環己酮之1 : 1溶液）、4份當作硬化觸媒的乙醯丙酮化鈷 (Π)(東京化成（股）製，固體成分1 %的DMF溶液） 、及40份的球形矽石（S0C2 )，在高速旋轉混合機中均 勻分散，以製作樹脂清漆。於厚度38 μιη的PET薄膜上， 藉由口模式塗佈機來塗佈上述清漆，使用熱風乾燥爐來去 除溶劑，製作硬化性樹脂組成物層的厚度爲40μιη的黏著 薄膜。 藉由與實施例2同樣的方法，由上述黏著薄膜在電路 基板上形成硬化性樹脂組成物層。然後，藉由與實施例2 同樣的方法，經由實施例1記載的金屬膜轉印用薄膜，將 金屬膜轉印到絕緣層上，藉由電（電解）鍍銅來形成鍍銅 層’以製作多層印刷配線板。支持體層的剝離性係良好地 以手能容易剝離。又，金屬膜層係被均句轉印，沒有見到 樹脂與金屬層間的起泡、金屬層的皺紋、金屬層的龜裂等 異常。 [實施例4] <改性聚醯亞胺的調製> 於反應容器中’混合50克G-3 000 ( 2官能性羥基末 端聚丁二烯，數量平均分子量=5〇47 (GPC法），羥基當 量=1 798g/eq.，固體成分l〇〇w%:日本曹達（股）製）、 23‘5克Ipz〇le 150 (芳香族烴系混合溶劑：出光石油化學 -40- 200904283 (股）製）、0.0 0 7克月桂酸二丁錫，使均勻溶解。當變 成均勻時，升溫到50°C，再邊攪拌邊添加4.8克甲苯-2,4-二異氰酸酯（異氰酸酯基當量=8 7.08 g/eq.)，進行約3小 時的反應。接著，將此反應物冷卻到室溫爲止，然後於其 中加入 8.83 克二苯甲酮四羧酸二酐（酸酐當量 = 161 .lg/eq. )、〇.〇7克三伸乙二胺及74.09克乙基二甘醇 醋酸酯（DAICEL化學工業（股）製），邊攪拌邊升溫到 l3〇°C爲止，進行約4小時的反應。在以FT-IR確認 22 5 0CHT1的NCO峰消失之時間點，更添加1.43克甲苯-2,4-二異氰酸酯（異氰酸酯基當量=8 7.0 8 g/eq.)，再於 13 0°C邊進行2〜6小時的攪拌反應，邊以FT-IR來進行 N C Ο峰消失的確認。確認NC 0峰的消失，視爲反應的終 點’將其降溫到室溫爲止，然後以1 〇 〇網目的濾布來進行 過濾，得到改性聚醯亞胺樹脂。 改性聚醯亞胺樹脂的性質狀態： 黏度= 7.0Pa.s ( 25°C, E型黏度計） 酸價=6.9mgKOH/g 固體成分= 40w% 數量平均分子量=19890 聚丁二烯構造部分的含有率=50x 1 00/ ( 5〇 + 4.8 + 8.8 3 + 1.43 ) =76.9 質量 ％ <黏著薄膜的製作> 混合4 0份的上述改性聚醯亞胺樹脂清漆、4份的液狀 -41 - 200904283 雙酚A型環氧樹脂（828EL) 、12份的含有二環戊二稀之 多官能環氧樹脂（環氧當量279，大日本油墨化學工業（ 股）製「HP-7200H」）、8_5份的苯酚酚醛清漆樹脂（固 形物的酚性羥基當量1 2 0，大日本油墨化學工業（股）製 「TD-2090」，固體成分60%的MEK溶液）、及1〇份的 球形矽石（SOC2 )，在高速旋轉混合機中均勻分散’以 製作樹脂清漆。於厚度38μιη的PET薄膜上’藉由口模式 塗佈機來塗佈上述清漆，使用熱風乾燥爐來去除溶劑’製 作硬化性樹脂組成物層的厚度爲40 μιη的黏著薄膜。 藉由與實施例2同樣的方法，由上述黏著薄膜在電路 基板上形成硬化性樹脂組成物層。然後，藉由與實施例2 同樣的方法，經由實施例1記載的金屬膜轉印用薄膜，將 金屬膜轉印到絕緣層上，藉由電（電解）鍍銅來形成鍍銅 層，以製作多層印刷配線板。支持體層的剝離性係良好地 以手能容易剝離。又，金屬膜層係被均勻轉印，沒有見到 樹脂與金屬層間的起泡、金屬層的皺紋、金屬層的龜裂等 異常。 [實施例5] 除了金屬膜轉印用薄膜的金屬膜層係僅由5 0 〇nm的銅 層所構成（無鉻層）以外，藉由與實施例2同樣的方法， 製作多層印刷配線板。支持體層的剝離性係良好地以手能 容易剝離。又’金屬膜層係被均勻轉印，沒有見到樹脂與 金屬層間的起泡、金屬層的皺紋、金屬層的龜裂等異常。 -42 - 200904283 [實施例6] 除了金屬膜轉印用薄膜的金屬膜層係僅由25 Onm的銅 層所構成（無鉻層）以外，藉由與實施例2同樣的方法’ 製作多層印刷配線板。支持體層的剝離性係良好地以手能 容易剝離。又，金屬膜層係被均勻轉印，沒有見到樹脂與 金屬層間的起泡、金屬層的皺紋、金屬層的龜裂等異常。 [實施例7] <金屬膜轉印用薄膜的製作> 於厚度38 μιη的聚對苯二甲酸乙二酯（以下簡稱PET )薄膜上，藉由口模式塗佈機來塗佈Plascoat Z-561 (互 應化學工業（股）製）的固體成分2·5 %之甲基乙基酮（ 以下簡稱ΜΕΚ)與Ν,Ν-二甲基甲醯胺（以下簡稱DMF) 的1 : 1溶液’使用熱風乾燥爐從室溫到1 2 0。(3使乾燥1 5 分鐘以去除溶劑’在PET薄膜上形成1 μιη的水溶性聚酯 樹脂層。接著’於水溶性聚酯樹脂層上藉由濺鍍（Ε_ 400S，Canon-Anelva (股）製）來形成5 00nm的銅層，再 於該銅層上形成20nm的鉻層，以製作5 20nm的金屬膜層 之金屬膜轉印用薄膜。 <黏著薄膜的製作> 於1 5份的MEK與1 5份的環己酮之混合液中，邊攪 拌邊加熱溶解2 8份的液狀雙酚a型環氧樹脂（環氧當量 -43- 200904283 180,日本環氧樹脂（股）製「Epi coat 8 2 8EL」）及28份 的萘型4官能環氧樹脂（環氧當量163，大日本油墨化學 工業（股）製「HP4700」）。於其中混合50份的酚系硬 化劑即含三畊構造的酚醛清漆樹脂（固形物的酚性羥基當 量120，大日本油墨化學工業（股）製「LA7052」，固體 成分60%的MEK溶液）、20份的苯氧樹脂（分子量 50000,日本環氧樹脂（股）製「E 1 2 5 6」固體成分40%的 MEK溶液）、〇 1份的硬化觸媒（2E4MZ ) 、55份的球形 矽石（SOC2 ) ' 30份的聚乙烯縮丁醛樹脂（積水化學工 業（股）製「KS-1」）、3份的具有丁二烯構造之環氧樹 脂（分子量27000, DAICEL化學工業（股）製「P B - 3 6 0 0 」），在高速旋轉的混合機中均勻分散，製作樹脂清漆。 於厚度38μπι的PET薄膜上，藉由口模式塗佈機塗佈上述 清漆，使用熱風乾燥爐來去除溶劑，製作硬化性樹脂組成 物層的厚度爲40μπι的黏著薄膜。 <藉由黏著薄膜在電路基板上形成硬化性樹脂組成物層> 於以18μιη厚的銅層形成電路的玻璃環氧樹脂基板之 銅層上，用 CZ8100 (含有唑類的銅錯合物、有機酸的表 面處理劑（MEC (股）製））來處理而施予粗化，以與銅 電路表面接觸的方式，使用分批式真空加壓層壓機1^乂1^-5 〇 〇 ((股）名機製作所製商品名），將上述黏著薄膜層 壓於電路基板的兩面。層壓係減壓30秒，在13hPa以下 的氣壓進行。接著，冷卻到室溫後，剝離黏著薄膜的支持 -44 - 200904283 體層，在電路基板的兩面上形成硬化性樹脂組成物層。 <藉由金屬膜轉印用薄膜來轉印金屬膜> 以金屬膜層接觸上述硬化性樹脂組成物層的方式，將 上述金屬膜轉印用薄膜層壓合於電路基板。層合係藉由使 用分批式真空加壓層壓機MVLP-5 00 ((股）名機製作所 製商品名），層壓於電路基板的兩面上而進行。層壓係減 壓30秒，使氣壓成爲13hPa以下，然後藉由30秒、 7.54kgf/cm2的壓力下進行加壓而進行。之後，將硬化性 樹脂組成物層在150 °C硬化30分鐘，再於180 °C硬化30分 鐘，以形成絕緣層（硬化物層）。由該絕緣層剝離金屬膜 轉印用薄膜的支持體層即PET薄膜。剝離性係良好地以手 能容易剝離。然後，以40°C的10%氫氧化鈉水溶液來溶解 去除水溶性聚酯層。金屬膜層係被均勻轉印，沒有見到樹 脂與金屬層間的起泡、金屬層的皺紋、金屬層的龜裂等異 常。 <鍍銅層形成> 於金屬膜層上進行電（電解）鍍銅，形成約3 0 μιη厚 的鍍銅層，以製作多層印刷配線板。 [實施例8] <金屬膜轉印用薄膜的製作>200904283 IX. The present invention relates to a film for transfer of a metal film, a method for transferring a metal film, and a method for producing a circuit board, and more particularly to a flexible printed wiring board, a multilayer printed wiring board, or the like. In the manufacture of a circuit board, a film for transferring a metal film for forming a metal layer as a layer for forming a conductor layer on a surface of an insulating layer, a method of transferring a metal film from the film, and a method of using the film A method of manufacturing a circuit board. [Prior Art] A circuit board such as a multilayer printed wiring board or a flexible printed wiring board, which is widely used in various electronic devices, is required to be thinner or to have fine wiring of circuits for miniaturization and high performance of electronic equipment. Chemical. Therefore, as a method for producing the same, for example, it is known that a curable resin composition is laminated on an inner layer circuit board by an adhesive film, and the curable resin composition is cured to form an insulating layer, followed by alkaline permanganese. The insulating layer is roughened by an oxidizing agent such as a potassium acid solution, and a plating layer is formed on the rough surface by electroless plating, followed by electrolytic plating to form a semi-addition of the conductor layer. Here, in order to obtain a conductor layer having a high adhesion strength, in the above method, an oxidizing agent is required to roughen the surface of the insulating layer (forming irregularities on the surface), and an anchoring effect is obtained between the conductor layer and the conductor layer, but when the circuit is formed When the unnecessary plating layer is removed by etching, it is difficult to remove the sheet layer of the anchor portion, and when the engraving is performed under the condition that the sheet portion of the anchor portion can be sufficiently removed, the dissolution pattern of the wiring pattern is marked, and the micro wiring is generated. The problem of hindrance. -5- 200904283 Therefore, as a method for solving such a problem, a method of forming a metal film layer on a substrate by transfer has been attempted. In this case, a metal film layer is formed on the support by vapor deposition or the like to form a transfer film, and the metal film layer of the transfer film is transferred onto the resin composition layer on the base plate. A method of forming a conductor layer on the transferred metal film layer by plating or the like on the surface of the (insulating layer) or the surface of the prepreg. For example, a method of using a transfer film using a fluororesin, an olefin resin, or a polyvinyl alcohol resin as a release layer has been reported (Patent Document 1), and an adhesive resin containing an acrylic resin or a melamine resin is used. The adhesive is used as a film for transfer of a release layer (Patent Document 2). [Patent Document 1] JP-A-2002-324969 (Patent Document 2) JP-A-2002-324969 SUMMARY OF INVENTION [Problems to be Solved by the Invention] However, in the embodiment of Patent Document 1, the release layer is In the transfer film using a fluororesin, the copper film is transferred onto the polyimide film via an epoxy-based adhesive. However, in order to obtain good transferability, it is necessary to form an epoxy-based adhesive and a copper film. It is difficult to transfer the surface of the attached body (resin composition layer or prepreg on the substrate) having a relatively low adhesiveness with high adhesion. Further, at the time of transfer, the resin composition layer or the prepreg is hardened. Although the adhesion to the metal film layer can be improved, the present inventors attempted to use a polyparaphenylene with a fluororesin-based release layer. A film for transfer of a film of ethylene dicarboxylate (PET) film, which transfers a copper film to a resin composition layer, and a peeling of the PET film from the copper film adhered to the layer of the cured resin composition, -6-200904283 The peelability is poor, and the transfer of a uniform copper film is difficult. Further, the inventors of the present invention have attempted to transfer a copper film to a resin composition layer by using a polyvinyl alcohol resin in a release layer as disclosed in Patent Document 1, but copper adhered from the cured resin composition layer. It is difficult to peel off the p ET film. Further, the inventors of the present invention have attempted to carry out the resin composition layer by a PET film with an acrylic resin-based release layer and a PET film with a melamine resin-based release layer as disclosed in Patent Document 2. The copper film is transferred, but the peeling property of the peeled PET film is still poor from the copper film adhered to the cured resin composition layer, and the transfer system of the uniform copper film is difficult. Therefore, the problem to be solved by the present invention is to provide a film for transfer of a metal film having excellent metal film layer transferability, and a method for efficiently producing a circuit board using the film for transfer of the metal film. (Means for Solving the Problem) In order to solve the above-mentioned problems, the inventors of the present invention have conducted a review of the above-mentioned problems, and as a result, it has been found that a water-soluble cellulose resin layer, a water-soluble polyester resin layer or a release layer is used for the release layer of the film for metal film transfer. The water-soluble acrylic resin layer, for example, in the circuit board manufacturing step, 'overlapped metal film transfer film' on the surface of the curable resin composition layer on the substrate and the metal film layer contacting the surface of the resin composition layer The resin composition layer is hardened, so that the support layer can be easily peeled off at the interface with the release layer and then the release layer present on the metal film layer can be removed by the aqueous solution. The metal film layer is not uneven, but may have Efficient transfer, uniform metal film layer transfer system becomes possible 200904283 'Complete the present invention. η卩, the present invention includes the following contents. (1) A film for transfer of a metal film, comprising: a support layer; and one or more selected from the water-soluble cellulose resin, the water-soluble polyester resin, and the water-soluble acrylic resin on the support layer a release layer formed of a water-soluble polymer, and a metal film layer formed on the release layer. (2) The film for metal film transfer according to (1) above, wherein the release layer is a water-soluble cellulose resin layer. (3) The film for metal film transfer according to (1) or (2) above, wherein the water-soluble cellulose resin layer is hydroxypropylmethylcellulose phthalate or hydroxypropylmethylcellulose One or two or more selected from the group consisting of acetate succinate and hydroxypropyl methylcellulose acetate phthalate. (4) The film for metal film transfer according to any one of (1) to (3), wherein the support layer is a plastic film. (5) The film for metal film transfer according to any one of (1) to (3), wherein the support layer is a polyethylene terephthalate film. (6) The film for metal film transfer according to any one of (1) to (5) wherein the metal film layer is made of chromium, nickel, titanium, nickel-chromium alloy, aluminum, gold, silver, and copper. One or more layers formed of the metals selected by the group are formed. (7) The film for metal film transfer according to any one of the above aspects, wherein the metal film layer is formed of copper. (8) The metal film of the above-mentioned (1) to (5), wherein the metal film layer is formed with a copper layer, a chromium layer, and a nickel on the release layer in this order. - Chrome alloy layer or titanium layer. (9) The film for metal film transfer according to any one of the above aspects, wherein the metal film layer is formed by a vapor deposition method or/and a sputtering method. (1) The film for metal film transfer according to any one of the above aspects, wherein the thickness of the support layer is ΙΟμηη to 70 μmη. The film for metal film transfer according to any one of the above aspects, wherein the layer thickness of the release layer is Ο.ίμιη~20μιη. The film for metal film transfer according to any one of the above aspects, wherein the layer thickness of the release layer is 〇.2 μm to 5 μm. (1) The film for metal film transfer according to any one of the above aspects, wherein the metal film layer has a layer thickness of 50 nm to 5000 nm. The film for metal film transfer according to any one of the above aspects, wherein the metal film layer has a layer thickness of 50 nm to 100 nm. (15) A method for transferring a metal film layer, comprising at least a method in which a surface layer is formed of a curable resin composition, and a metal film layer is in contact with a surface of the object to be attached, and the above is overlapped ( The film for metal film transfer according to any one of (1), wherein the step of curing the curable resin composition, the step of peeling off the support layer, and the dissolution of the metal film layer by the aqueous solution are removed. The steps of the layer. (16) A method of producing a circuit board, comprising: laminating the above (1) to (14) on a layer of a curable resin composition on a substrate so that a surface of the curable resin composition layer is in contact with the metal film layer; The film for metal film transfer described in any one of -9 - 200904283, the step of curing the curable resin composition, the step of peeling off the support layer, and the dissolution of the release layer present on the metal film layer by the aqueous solution The steps. (1) The method according to the above (1), wherein the curable resin composition layer is composed of a prepreg in which a sheet-like substrate made of fibers is impregnated with a curable resin composition. (1) The method according to the above (16) or (17), wherein after the step of dissolving and removing the release layer in an aqueous solution, the step of forming a conductor layer by plating on the metal film layer is further included. (19) A method for producing a metal-clad laminate, characterized in that a metal film layer is contacted with a prepreg on one or both sides of a multilayer prepreg which is superposed by a single prepreg or a plurality of prepregs. The film for metal film transfer according to any one of the above (1) to (1), which is superimposed on the surface of the body. (2) A circuit board produced by transferring a metal film layer using the film for metal film transfer according to any one of the above (1) to (1). (21) A metal-clad laminate according to any one of the above (1) to (14), which is produced by transferring a metal film layer. (Effect of the invention) The film for metal film transfer according to the present invention has excellent metal film layer transferability, so that a uniform metal film layer transfer system is possible. -10-200904283 Therefore, when the film for metal film transfer of the present invention is used in the production of a circuit board, the surface of the insulating layer is not roughened by an oxidizing agent such as an alkaline potassium permanganate solution, and the surface can be formed on the surface. Since the metal film layer having high adhesion and uniformity can be formed, the etching in the circuit formation can be performed under milder conditions. As a result, the wiring of the circuit board such as the multilayer printed wiring board or the flexible printed wiring board is finely wired. Excellent results. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to preferred embodiments. The film for metal film transfer of the present invention (hereinafter simply referred to as "film") has a support layer, a release layer formed on the support layer, and a metal film layer formed on the release layer. <Support layer> In the film for metal film transfer of the present invention, the support layer has a self-supporting film or sheet, and a plastic film can be suitably used. Examples of the plastic film include a polyethylene terephthalate film, a polyethylene naphthalate film, a polyimide film, a polyimide film, a polyamide film, and a polytetrafluoroethylene film. The polycarbonate film or the like is preferably a polyethylene terephthalate film or a polyethylene naphthalate film, and particularly preferably an inexpensive polyethylene terephthalate film. The surface of the support film on the side in contact with the water-soluble polymer release layer may be subjected to a release treatment such as a release agent such as a polyfluorene-based release agent, an alkyd-based release agent, or a fluorine-based release agent. Electricity-11 - 200904283 Surface treatment such as halo treatment. Further, a surface treatment such as matting treatment or corona treatment may be applied to the surface of the support film on the side not in contact with the water-soluble polymer. Further, the layer thickness of the support layer is usually ΙΟμηη to 70 μmη, preferably 15 μm to 70 μm. If the layer thickness is too small, workability is poor, and the peeling property of the support layer or the smoothness of the metal film layer tends to be lowered. If the layer thickness is too large, the cost is unfavorable and not practical. < Release layer> The release layer is one or more kinds of water-soluble polymers selected from water-soluble cellulose resins, water-soluble polyester resins, and water-soluble acrylic resins. Among them, it is more preferably a water-soluble cellulose resin or a water-soluble polyester resin, and particularly preferably a water-soluble cellulose resin. Usually, in the water-soluble polymer release layer, any of the water-soluble polymers alone may be used, or two or more kinds of water-soluble polymers may be mixed and used. Further, the water-soluble polymer release layer is usually formed in a single layer, but may have a multilayer structure in which two or more layers of water-soluble polymers to be used are different from each other. (Water-Soluble Cellulose Resin) The "water-soluble cellulose resin" as used in the present invention is preferably a cellulose ether or a cellulose ether ester which is a cellulose derivative which imparts a treatment for imparting water solubility to cellulose. Wait. The cellulose ether refers to one or more hydroxyl groups present in the mono-12-200904283 position of one or more of the cellulose anhydrides in order to give one or more ether linkage groups to the cellulose polymer. The ether formed is converted; in the ether linkage group, one selected from the group consisting of a hydroxyl group, a carboxyl group, an alkoxy group (carbon number 1 to 4), and a hydroxyalkoxy group (carbon number 1 to 4) is usually used. The alkyl group (carbon number 1 to 4) substituted with the above substituent. Specifically, a hydroxyalkyl group (carbon number: 1 to 4) such as 2-hydroxyethyl group, 2-hydroxypropyl group or 3-hydroxypropyl group; 2-methoxyethyl group, 3-methoxypropyl group; Alkoxy group (carbon number 1 to 4) alkyl group (carbon number 1 to 4); 2-(2-hydroxyethoxy)ethyl group; 2-methoxypropyl group; 2-ethoxyethyl group; a hydroxyalkyloxy group (carbon number: 1 to 4) alkyl group (carbon number: 1 to 4) such as a 2-(2-hydroxypropoxy)propyl group, or a carboxyalkyl group such as a carboxymethyl group (carbon number 1) ~4) etc. The ether linkage group in the polymer molecule may be a single species or a plurality of species. Namely, it may be a cellulose ether having a single ether linkage group, or a cellulose ether having a plurality of ether linkage groups. Specific examples of the cellulose ether include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxybutyl methyl cellulose, and hydroxyethyl ethyl cellulose. And carboxymethylcellulose and such water-soluble salts (for example, alkali metal salts such as sodium salts). Further, the average number of moles of the substituted ether group per unit of the glucose ring of the cellulose ether is not particularly limited, and is preferably from 1 to 6. Further, the molecular weight of the cellulose ether is preferably from about 20,000 to about 60,000 in terms of a weight average molecular weight. On the other hand, a cellulose ether ester is formed by forming between one or more hydroxyl groups present in cellulose and one or more suitable organic acids or reactive derivatives thereof, thereby forming in a cellulose ether. An ester linkage ester. In addition, the "cellulose ether" as used herein is as described above, the "organic acid" includes an aliphatic or aromatic carboxylic acid (carbon number 2 to 8), and the aliphatic carboxylic acid may be an acyclic-13-200904283 ( Branched or non-branched) or cyclic, or saturated or unsaturated. Specifically, 'as an aliphatic carboxylic acid, for example, a substituted or unsubstituted non-acrylic acid, butyric acid, valeric acid, malonic acid, succinic acid, glutaric acid, fumaric acid, maleic acid or the like may be mentioned. A cyclic aliphatic dicarboxylic acid; a non-cyclic aliphatic hydroxy group such as glycolic acid or lactic acid; or a non-cyclic aliphatic hydroxy group such as malic acid, tartaric acid or citric acid, or a dicarboxylic acid. Further, the aromatic carboxylic acid is preferably an aromatic carboxylic acid having 14 or less carbon atoms, and particularly preferably an aryl group having a phenyl group or a naphthyl group or the like having at least one carboxyl group (for example, 1, 2 or 3 carboxyl groups). Aromatic carboxylic acid. Further, the aryl group may be the same or different one or more (for example, 1, 2 or 3) groups selected from a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms (for example, a methoxy group) and a sulfonyl group. Replace. In a suitable example of the aromatic carboxylic acid, phthalic acid, isophthalic acid, terephthalic acid or trimellitic acid (1,2,4-benzenetricarboxylic acid) or the like can be given. When the organic acid has one or more carboxyl groups, it is preferred that only one carboxyl group of the acid forms an ester linkage to the cellulose ether. For example, in the case of hydroxypropylmethylcellulose succinate, one carboxyl group of each succinate group is ester-linked to cellulose, and the other carboxyl group is present as a free acid. The "ester linkage" is formed by the reaction of cellulose or a cellulose ether with a suitable organic acid or a reactive derivative thereof. Among suitable reactive derivatives are, for example, acid anhydrides such as phthalic anhydride. The ester linking group in the polymer molecule may be single or plural. Namely, it may be a cellulose ether ester having a single ester linking group, or may be a cellulose ether ester having a plurality of ester linking groups. For example, 'hydroxypropyl methylcellulose acetate succinate has hydroxypropyl methylcellulose with both ester-ester and acetate-ester. Suitable cellulose ether ester hydroxypropyl group Specific examples of the ester of the cellulose cellulose include hydroxypropylmethylcellulose acetaminocellulose succinate, hydroxypropylmethylcellulose vinegar, and hydroxypropylmethylcellulose phthalate. Hydroxypropyltriglyceride, hydroxypropylmethylcellulose acetate phthalic acid cellulose acetate trimellitate, hydroxypropyl cellulose ester, hydroxypropyl cellulose butyrate The acid ester, the hydroxy acid ester phthalate succinate, the hydroxypropyl cellulose acetate succinate, etc., may be used alone or in combination of two or more, preferably hydroxypropylmethylcellulose benzene. The formic acid vinegar, the transester acetate succinate, the hydroxypropyl methylcellulose acetate oxime is not particularly limited, and is preferably 5%. The molecular weight of the cellulose ether vinegar is about ten to 60,000 by weight average molecular weight. The method for preparing cellulose ether and cellulose ether ester is widely used as a raw material, and is obtained by reacting a chemical agent or an esterifying agent, but in the present invention, for example, Shin-Etsu Chemical Industry (for example) The company is made of "HP_55", which is hydroxypropylmethylcellulose phthalate). (Water-soluble polyester resin) t mixed ester. Or hydroxypropyl cellulose ester, hydroxypropyl acid succinate cellulose phenyl hydroxy ester, hydroxypropyl methyl acetate phthalonitrile cellulose acetate trimellitic acid. Among them, propylmethylcellulose phthalic acid ester replaces the ester group to about -2%. Further, it is preferably 20,000 known, and a commercially available product can be used in combination with ether. "Hb-50-200904283" as used in the present invention means a polyvalent carboxylic acid or an ester-forming derivative thereof and a polyhydric alcohol or an ester-forming derivative thereof as a main raw material. A polyester resin formed by a linear polymer, which is synthesized by a usual polycondensation reaction, has a hydrophilic group introduced into a molecule or a molecular end. Here, as a hydrophilic group, a sulfonic acid group, a carboxyl group, and a phosphoric acid group The organic acid group such as a group or a salt thereof is preferably a sulfonic acid group or a salt thereof, a carboxyl group or a salt thereof. The water-soluble polyester resin is particularly preferably a sulfonic acid group or a salt thereof and/or a carboxyl group or a salt thereof. Representative examples of the polyvalent carboxylic acid component of the polyester resin include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalene dicarboxylic acid, and 1,4-cyclohexane. Dicarboxylic acid, adipic acid, etc. may be used singly or in combination of two or more kinds thereof. Further, together with the above various compounds, a hydroxycarboxylic acid such as p-hydroxybenzoic acid or maleic acid may be used in a small amount. An unsaturated carboxylic acid such as fumaric acid or itaconic acid. As a polyol component of the polyester resin The table 'has ethylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexane methanol, benzene dimethyl The diol, dimethylolpropionic acid, glycerin, trimethylolpropane or poly(tetramethylene oxide) diol may be used singly or in combination of two or more. The introduction of a hydrophilic group in the molecule or at the end of the molecule can be carried out by a well-known conventional method, which is preferably a method of copolymerizing a vinegar-forming compound containing a hydrophilic group (for example, an aromatic carboxylic acid compound, a trans group compound, etc.). For example, when introducing a sulfonate group, it is preferred to copolymerize from 5 _sulfonic acid phthalic acid, 5 sulfonate ammonium isophthalic acid, sodium 4-sulfonate phthalic acid-16-200904283 , 4-methyl methanesulfonate isophthalic acid, sodium 2-sulfonate terephthalic acid, potassium 5-sulfonate isophthalic acid, potassium 4-sulfonate isophthalic acid and potassium 2-sulfonate One or more selected dicarboxylic acids, etc. Further, when a carboxyl group is introduced, for example, it is preferred to copolymerize from trimellitic anhydride, trimellitic acid, and pyromellitic anhydride. One or more selected ones of tetraacid, trimesic acid, cyclobutane tetracarboxylic acid, dimethylolpropionic acid, etc., after the copolymerization reaction, by amine compound, ammonia or alkali metal salt The carboxylate group may be introduced into the molecule, and the molecular weight of the water-soluble polyester resin is not particularly limited, and the weight average molecular weight is preferably about 10,000 to 40,000. If the weight average molecular weight is less than 1,000,000, the layer is In the present invention, a commercially available product can be used as the water-soluble polyester resin, and, for example, a mutual chemical industry can be used. "Plascoat Z_561" (weight average molecular weight: about 27,000), "Plascoat Z-565" (weight average molecular weight: about 25,000), and the like. (Water-soluble acrylic resin) The "water-soluble acrylic resin" as used in the present invention means an acrylic resin containing a thiol group-containing monomer as an essential component and dispersed or dissolved in water. The gastric acrylic resin is more preferably an acrylic polymer containing a carboxyl group-containing monomer and (meth) propylene as a necessary monomer component, and optionally containing another unsaturated monomer as a monomer component. -17- 200904283 Among the above monomer components, examples of the carboxyl group-containing monomer include (meth)acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, and maleic anhydride. Further, one or two or more of these may be used, and the monomethyl maleate, the monobutyl maleate, the monomethyl isonate, and the monobutyl yaconate. Among these, (meth)acrylic acid is preferred. Further, examples of the (meth) acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and n-butyl (meth)acrylate. Isobutyl acrylate, n-amyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethyl (meth)acrylate The carbon number of the alkyl group such as hexyl hexyl ester, decyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and octadecyl (meth) acrylate is 1 to 18 One or two or more of these may be used as the alkyl methacrylate. Further, examples of the other unsaturated monomer include an aromatic alkenyl compound, a acrylonitrile compound, a conjugated diene compound, a halogen-containing unsaturated compound, and a hydroxyl group-containing monomer. Examples of the aromatic alkenyl compound include the present ethylene, α-methylstyrene, p-methylstyrene, and p-methoxy basic ethylene. Examples of the acrylonitrile compound' include acrylonitrile and a methacrylonitrile temple. Examples of the conjugated diene compound include butadiene and isoprene. Examples of the halogen-containing unsaturated compound include vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropene, and vinylidene fluoride. Examples of the hydroxyl group-containing monomer include (meth)acrylate 2-hydroxyethyl ester, (-18-200904283 methyl)acrylic acid 2-hydroxypropyl ester, and (meth)acrylic acid 3-hydroxypropyl ester group. 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, methyl propyl hydroxylate, α-hydroxymethyl ethyl (meth) acrylate, and the like. One or two or more of these. As described later, in the present invention, the release layer is preferably formed by applying a cellulose resin, a water-soluble polyester resin or a water-soluble acrylic resin solution onto a support and drying it. In the case of a soluble acrylic resin, the coating liquid may be in the form of an emulsion or an aqueous solution. When a water-soluble acrylic resin is used in the form of an emulsion, a preferred emulsion; in the core-shell emulsion, a carboxyl group is important in the shell of the core-shell particle, and therefore, the shell is composed of a monomer containing a carboxyl group and The acrylate resin is composed of an acrylic resin. The dispersion of the core-shell particles (emulsion) can be, for example, Joncryl 7600 (Tg: about 35 ° C), 7630 约 about 53 ° C, and 5 3 8 J ( Tg: about 66 ° C), 3 52D (Tg: about (both manufactured by BASF Japan Co., Ltd.), etc. When a water-soluble acrylic resin is used in the form of an aqueous solution, the resin contains a carboxyl group-containing monomer and (A) The acrylate acrylate is relatively important in molecular weight. Therefore, the weight average molecular weight is 1000 to 50000, and if the weight average molecular weight is less than 1,000, the property tends to decrease, and the weight average molecular weight exceeds 50,000. The adhesion is high, and the peeling property of the support after hardening tends to be. (Methylic acid 4- can be used as a core-based base for water-soluble fat-soluble coating). 5 6〇C) Acrylate tree For the formation of a preferred layer, a commercially available product can be used as the aqueous solution of the water-soluble acrylic resin such as -19-200904283. For example, J〇ncryl 354J (manufactured by BASF Japan Co., Ltd.) or the like can be used. In the emulsion and aqueous solution of the water-soluble acrylic resin, the emulsion is easily thinned due to its high molecular weight. Therefore, it is preferably an emulsion of a water-soluble acrylic resin. In the present invention, the method of forming the release layer on the support layer is not particularly A well-known lamination method, such as a hot press, a hot roll laminator, an extrusion laminator, and application/drying of a coating liquid, can be used, but it is easy to form a layer with high property uniformity. In view of the above, a coating liquid containing a water-soluble cellulose, a water-soluble polyester or a water-soluble acrylic resin and a method of drying are preferably used. In the present invention, the release layer may be a single layer or a plurality of layers ( That is, it may be composed of at least one layer selected from the water-soluble cellulose layer, the water-soluble polyester resin layer, and the water-soluble acrylic resin layer, or may be composed of two or more layers (laminated layer). The layer thickness of the release layer is usually Ο.ίμιη~20μπι, preferably 0.2μιη~ ΙΟμιη, more preferably 0.2~5μιη. The "layer thickness" as used herein is when the release layer is a single layer. It refers to the thickness of the multilayer. In the case of multiple layers, it refers to the total thickness of the multilayer. If the layer thickness is too thin, the peelability of the support layer is reduced. If the layer thickness is too thick, the hardened resin composition layer is thermally hardened. At the time of the thermal expansion rate of the metal film layer and the mold release layer, there is a problem that cracks or scratches occur in the metal film layer. <Metal film layer> -20- 200904283 As the metal film layer, a metal monomer such as gold, silver, silver, copper, cobalt, chromium, nickel, titanium, tungsten, iron, tin, indium, or the like can be used, and suitably All kinds of metals such as solid solution (alloy) of two or more types of metals, and chromium, nickel, titanium, and nickel are preferable from the viewpoints of cost, vapor deposition method, or versatility and conductivity of sputtering method. -Chromium alloy, aluminum, gold, silver, and copper are particularly preferred for copper when used for wiring of circuit boards. Further, the metal film layer may be composed of a single layer or a laminate of two or more layers of different metals. For example, when a circuit board is manufactured using the film, a copper layer is laminated on the surface of the resin composition layer on the substrate or the surface of the prepreg, and in the step of thermally curing the resin composition layer or the prepreg, In order to prevent the resin from thermally degrading (decomposing) or the like due to the diffusion of copper into the resin composition or the prepreg, a chromium layer, a nickel-chromium alloy layer or a titanium layer may be provided on the copper layer as needed. That is, after the copper layer is formed on the water-soluble polymer release layer, a complex layer, a nickel-chromium layer or a titanium layer can be formed. The method of forming the metal film layer is preferably formed by a sputtering method or/and a vapor deposition method from the viewpoint of film properties and adhesion to the curable resin composition layer. The layer thickness of the metal film layer is not particularly limited, and is usually 5 〇ηηη to 5000 nm, preferably 50 nm to 30 Å, more preferably 100 nm to 3000 nm, and particularly preferably 100 nm to 100 Å. When the layer thickness is too small, defects in the formation of the uneven conductor layer may occur on the metal film layer due to damage or the like in the electrolytic plating operation in the production of the circuit board. On the other hand, if the layer thickness is too large, it takes a long time to form a metal film by a soldering method or/and a vapor deposition method, which is not preferable from the viewpoint of cost. In addition, when the two-layer structure of the copper layer/chromium layer, the nickel-chromium alloy layer or the titanium layer is as described above - 21 - 200904283, the entire layer thickness is the same as above, and the chromium layer, the nickel-chromium layer or The thickness of the titanium layer is preferably from 5 nm to 100 nm, more preferably from 5 nm to 50 nm', particularly preferably from 5 nm to 30 nm, most preferably from 5 to 20 nm. The transfer of the film for metal film transfer of the present invention to the metal film layer is attached to the object (the transfer target) formed of the curable resin composition on the surface layer by contact with the metal film layer. The film is laminated (laminated) in a manner of a surface of the body (transferred body), and after the curable resin composition is cured in this state, the support layer is peeled off, and the solution is dissolved in the metal film layer by an aqueous solution. The release layer is carried out. In other words, the metal film layer is strongly adhered to the object to be attached (the transfer target) by the curing of the curable resin composition, and the release layer remains on the metal film layer after the release of the support layer. However, since the release layer composed of the water-soluble cellulose layer, the water-soluble polyester resin layer or the water-soluble acrylic resin layer is dissolved and removed by an aqueous solution, the adherend and the metal film formed by the curable resin composition are formed. No foaming occurs between the layers, wrinkles, cracks, and the like which do not occur in the metal film layer, and the metal film layer can be uniformly transferred. Further, when peeling off before the hardening treatment, the metal film layer cannot be sufficiently transferred, and after the curing of the curable resin composition, the metal film layer is liable to cause cracks or the like. The curable resin composition is not particularly limited, and can be used for an epoxy resin, a cyanate resin, a phenol resin, a bismaleimide-triazine resin, a polyaniline resin, a propylene acid resin, A hardenable base resin such as a vinyl benzyl resin, which is a composition of at least a resin of the general hardener of the resin, -22-200904283. Further, a hardening accelerator may be further blended. The laminate of the film to the attached body is preferably laminated by a roll or a press machine from the viewpoint of workability and easy contact with the same contact state, thereby laminating the film. Treatment on the surface of the attached body. Among them, lamination is preferably carried out under reduced pressure by a vacuum lamination method. Further, the lamination method may be a batch type or a continuous type using a roll. The lamination conditions are generally preferably carried out under a reduced pressure of 20 mmHg (26.7 hPa) at a pressure of 1 to 1 lkgf/cm 2 (9·8 χ 104 to 107·9 χ 104 N/m 2 ). Pressure. For vacuum lamination, a commercially available vacuum laminator can be used. As a commercially available vacuum laminating machine, for example, a batch type vacuum pressure laminating machine MVLP-5 00 manufactured by Nippon Seiko Co., Ltd., a Vacuum Applicator of Nichigo-Morton Co., Ltd., Hitachi Industrial Co., Ltd. A drum type dry coater, a vacuum laminator made of AIC (share). In the present invention, as the aqueous solution for dissolving and removing the release layer on the metal film layer after peeling off the support layer, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide or the like is given as 0.5. ～10% by weight of an alkaline aqueous solution or the like dissolved in water. In general, the following is not necessary. However, in order to prevent problems in the production of a circuit board or the like, an alcohol such as methanol, ethanol or isopropyl alcohol may be contained in the water-soluble liquid φ. The method of dissolving and removing is not particularly limited, and for example, a method in which the substrate is rubbed and removed in an aqueous solution by dissolving and removing the substrate in the aqueous solution, and the solution is dissolved or removed in a spray or mist form. The temperature of the aqueous solution is usually from room temperature to 8 (TC), and the treatment time for water immersion, spraying, etc. can usually be carried out for 10 seconds - 23 - 200904283 for 10 minutes. As an aqueous solution, the alkali used in the manufacture of the circuit board can also be used. Image-type imaging solution (such as 〇. 5~2% by weight of sodium carbonate solution '25 °C~40 °C), dry film stripper stripping solution (for example, 1~5 wt% sodium hydroxide solution) , 4 0. <3 to 60 ° C), a swelling solution used in the desmear step (for example, an aqueous alkali solution containing sodium carbonate, sodium hydroxide, or the like, 60 ° C to 80 ° C). The object to be transferred (transferd body) to which the metal film layer of the film for metal film transfer of the present invention is transferred is not particularly limited as long as at least the surface layer thereof is composed of a curable resin composition. The film for metal film transfer of the present invention is particularly suitably used for forming a conductor layer in a manufacturing process of a circuit board such as a flexible wiring board or a multilayer printed wiring board. A method of producing a circuit board using the film for metal film transfer of the present invention is a method of the steps (A) to (C) below. (A) The film for metal film transfer of the present invention is laminated and laminated on the curable resin composition layer formed on the substrate so that the metal film layer contacts the surface of the curable resin composition layer, and the curable resin is composed. The layer is cured. Thereby, the metal film layer of the film for metal film transfer is adhered to the layer of the curable resin composition. (B) Next, the support layer of the film for metal film transfer is peeled off. The peeling of the support layer can be peeled off manually or mechanically by an automatic peeling device. (C) Next, the release layer existing on the metal film layer after removing the release support layer is dissolved in an aqueous solution. -24- 200904283 After the above steps (A) to (C), the transferred metal film layer is used as a conductor layer (wiring layer) as it is, or (D) is transferred to the metal film layer. On the other hand, a plating layer (wiring layer) is formed by plating (electroless plating and/or electrolytic plating) to further grow the metal layer. The metal layer formed by plating is usually the same metal type as the metal film layer, but a metal layer of a different metal type may be formed. As a suitable example, for example, when the metal film layer is a copper layer or a layer of a chromium layer or a nickel-chromium alloy layer is formed on the copper layer, copper plating is formed on the copper layer of the surface layer after transfer. The aspect of the layer. In the present invention, although the thickness of the plating layer depends on the thickness of the metal film layer and the design of the desired circuit substrate, it is generally 3 to 35 μm, preferably 5 to 3 0 μηι, as described in the present invention. Refers to a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a resin substrate, a thermosetting polyphenylene ether substrate, or the like, or has a pattern processing on one or both sides of the substrate ( In the case of manufacturing a circuit board, the conductor layer forming the circuit further includes a so-called "inner layer circuit board" which is suitable for forming an intermediate product of the insulating layer and the conductor layer. In addition, the "circuit board" of the present invention is not particularly limited as long as it has an insulating layer and a conductor layer forming a circuit, and various circuit boards such as a multilayer printed wiring board and a flexible printed wiring board are exemplified. In the present invention, as the curable resin composition used for the curable resin composition layer formed on the substrate, a conventionally known curable resin used as an insulating layer in a circuit board such as a multilayer printed wiring board can be used. The composition is not particularly limited, and for example, it can be used for epoxy tree-25 - 200904283 grease, cyanate resin, phenol resin 'shuangma quinone imine-three ploughing resin, polyimine resin, acrylic resin, The curable resin such as a vinyl benzyl resin is doped with at least a composition of a curing agent. From the viewpoint of adhesion to the metal film layer and insulation reliability, a composition containing at least (a) an epoxy resin, (b) a thermoplastic resin, and (c) a curing agent is preferable. Examples of the (a) epoxy resin include bisphenol a type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, and phosphorus. Epoxy resin, bisphenol s type epoxy resin, alicyclic epoxy resin, aliphatic lock epoxy resin, phenol novolac type epoxy resin 'cresol novolac type epoxy resin, bisphenol A novolac Epoxy resin, epoxy resin with butadiene structure, diglycidyl ether of bisphenol, diglycidyl ether of naphthalenediol, glycidyl ether of phenol, and diglycidyl ether of alcohol And alkyl substituted compounds, halides, hydrides, and the like of such epoxy resins. These epoxy resins may be used alone or in combination of two or more. Among these, from the viewpoint of heat resistance, insulation reliability, and adhesion to a metal film, the epoxy resin is preferably a bisphenol A type epoxy resin, a naphthalene type epoxy resin, or a naphthol type epoxy resin. An epoxy resin having a butadiene structure, a biphenyl type epoxy resin, or the like. Specifically, for example, a liquid bisphenol A type epoxy resin ("Epicoat 82 8EL" manufactured by Nippon Epoxy Co., Ltd.) or a naphthalene type bifunctional epoxy resin (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) HP4032", "HP4032D"), naphthalene-type 4-functional epoxy resin ("HP4700" manufactured by Dainippon Ink Chemicals Co., Ltd.), and naphthol-type epoxy resin (ESN-4 7 5V manufactured by Tohto Kasei Co., Ltd.) ) Epoxy resin having a butadiene structure -26- 200904283 ("PB-3600 j" manufactured by DAICEL Chemical Industry Co., Ltd.) and biphenyl type polyfunctional epoxy resin ("Naka 3 000H" manufactured by Nippon Kayaku Co., Ltd." , "NC3000L"),), biphenyl type epoxy resin ("YX4000" made by Nippon Epoxy Co., Ltd.). (b) The thermoplastic resin is blended for the purpose of imparting appropriate flexibility to the composition after curing, for example, phenoxy resin, polyvinyl acetal resin, polyimine, polyamidimide, poly Ether oxime, polyfluorene, and the like. These may be used alone or in combination of two or more. When the non-volatile content of the curable resin composition is 1% by mass, the thermoplastic resin is preferably blended at a ratio of 0.5 to 60% by mass, more preferably 3 to 50% by mass. When the blending ratio of the thermoplastic resin is less than 0.5% by mass, the viscosity of the resin composition is low, and it is difficult to form a uniform curable resin composition layer during coating and drying, and if it exceeds 60% by mass, The melt viscosity of the resin composition is high, and it tends to be difficult to embed the wiring pattern on the substrate. Specific examples of the phenoxy resin include FX280, FX293 manufactured by Tohto Kasei Co., Ltd., YX8100, YL6954, and YL6974 manufactured by Nippon Epoxy Resin Co., Ltd., and the like. The polyvinyl acetal resin is preferably a polyvinyl butyral resin, and as a specific example of the polyvinyl acetal resin, an electrochemical butyral 4000-2, 5000-A, 6000-manufactured by the Electrochemical Industry Co., Ltd. C, 6000-EP, Sekisui Chemical Industry Co., Ltd. S-LEC BH series, BX series, KS series, BL series, BM series, etc. Specific examples of the polyimine are Polyimine "Rikacoat SN20" and "Rikacoat PN20" manufactured by Shin-Nihon Chemical Co., Ltd. -27-200904283. Further, a linear polyimine obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (described in JP-A-2006-3 7083), and a polyfluorene A modified polyimine such as a polyimine of a oxyalkylene skeleton, which is described in JP-A-2002- 1 2667, JP-A-2000-3,196, and the like. Specific examples of the polyamidoximine are polyoxin imidates "Vylomax HR11NN" and "Vylomax HR16NN" manufactured by Toyobo Co., Ltd., and polyhethane oxides manufactured by Hitachi Chemical Co., Ltd. The skeleton of polyamidoximine "KS9100", "KS9300" and the like. Specific examples of the polyether oxime include polyether oxime "PES 5 003 P" manufactured by Sumitomo Chemical Co., Ltd., and the like. Specific examples of the poly-Maple include, for example, "P1700" and "P3500" manufactured by Solvay Advanced Polymers Co., Ltd. Examples of the (c) curing agent include an amine curing agent, an lanthanum curing agent, an imidazole curing agent, a phenol curing agent, a naphthol curing agent, an acid anhydride curing agent, or an epoxy adduct thereof. Or microencapsulated, cyanate resin, and the like. Among them, a phenol-based curing agent, a naphthol-based curing agent, and a cyanate resin are preferable. Further, in the present invention, the curing agent may be used alone or in combination of two or more. Specific examples of the phenolic curing agent and the naphthol-based curing agent include MEH-7700, MEH-78 10, MEH-785 1 (manufactured by Megumi Kasei Co., Ltd.), NHN, CBN, and GPH (Japanese medicine). (share) system, SN170, SN180, SN190, SN475, SN48 5, SN495, SN 3 7 5, -28- 200904283 SN3 95 (Dongdu Huacheng (share) system), LA7052, LA7054, LA 3018, LA1356 (Greater Japan Ink chemical industry (stock) system, etc. Specific examples of the cyanate resin include bisphenol A dicyanate and polyphenol cyanate (oligo(3-methylene-1,5-phenylene)), 4 , 4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4,-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2 , 2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanoester-3,5-dimethylphenyl)methane , 1,3-bis(4-cyanate phenyl-fluorene-(methylethylidene))benzene, bis(4-cyanate phenyl) sulfide, bis(4-cyanate phenyl) A polyfunctional cyanate resin derived from a bifunctional cyanate resin such as ether, a phenol novolac, a cresol novolak or the like, or a prepolymer obtained by trianomerization of a part of the cyanate resin. A commercially available cyanate resin may be a part of a phenol novolac type polyfunctional cyanate resin (manufactured by LONZA Co., Ltd., PT30, cyanate equivalent 124) or bisphenol A dicyanate or A prepolymer of all trimerized trimer (manufactured by LONZA Japan Co., Ltd., BA230, cyanate equivalent 232) and the like. (a) the compounding ratio of the epoxy resin to the (c) curing agent, in the case of a phenolic curing agent or a naphthol-based curing agent, the phenolic hydroxyl equivalent of such a curing agent for the epoxy equivalent of the epoxy resin It is preferably a ratio in the range of 0. 4 to 2.0, more preferably a ratio in the range of 0.5 to 1.0. In the case of the cyanate resin, the cyanate equivalent is preferably in the range of from 0.3 to 3.3, more preferably in the range of from 0.5 to 2.0, for the epoxy equivalent. When the reaction group equivalent ratio is outside this range, the mechanical strength or water resistance of the cured product tends to decrease. -29- 200904283 Further, in the curable resin composition, in addition to the (c) hardener, (d) a hardening accelerator may be further blended. Examples of such a curing accelerator include an imidazole compound and an organic phosphine compound. Specific examples thereof include 2-methylimidazole and triphenylphosphine. When the (d) hardening accelerator is used, it is preferably 0 to 1 to 3.0 mass% for the epoxy resin. The scope to use. Further, when a cyanate resin is used for the epoxy resin curing agent, for the purpose of shortening the curing time, it may be added as a curing catalyst in a system of an epoxy resin composition and a cyanate compound. The organometallic compound used. As an organometallic compound, an organic copper compound such as copper(II) acetoacetate, an organic zinc compound such as acetyl acetonide (II), cobalt(II) acetate, and cobalt(III) acetoacetate. Etc. organic cobalt compounds and the like. The amount of the organometallic compound to be added is usually from 10 to 500 ppm, preferably from 25 to 200 ppm, in terms of metal. Further, in the curable resin composition, (e) an inorganic chelating agent may be contained in order to reduce the thermal expansion of the composition after curing. Examples of the inorganic chelating agent include, for example, vermiculite, alumina, mica, mica, silicate, barium sulfate, magnesium hydroxide, titanium oxide, etc., preferably vermiculite or alumina. Meteorite. Further, from the viewpoint of insulation reliability, the average particle diameter of the inorganic ruthenium agent is preferably 3 μπ or less, and the average particle diameter is more preferably 丨.5 μηι or less. When the content of the inorganic chelating agent in the curable resin composition is 10% by mass based on the nonvolatile content of the curable resin composition, it is preferably 20 to 6 〇 mass ° / 〇, more preferably 2 0 ~50% by mass. When the content of the inorganic chelating agent is less than 20% by weight, the effect of lowering the coefficient of thermal expansion may not be sufficient. The -30-200904283 has no strength, and it is difficult to phosphatize or the like. The thickness of the system, blue, and enamel is also from the right side of the layer, and the harder condition is also 120. The lower the rising edge makes the system more suitable for the chemical tree than by the cloth liquid (the content of the machine sputum is more than 6 〇 weight%, In the curable resin composition, other components may be blended as needed. Examples of the component include an organic phosphorus-based flame retardant, an organic nitrogen-containing compound, and a nitrogen compound. a tackifier such as a polybenzazole-based flame retardant, a metal hydroxide fuel, a polyfluorene oxide powder, an Nylon powder, a fluorine powder, or the like (Orben) or a chlorinated polyether (Pent〇n). An anti-foaming agent or a leveling agent of a polyfluoride, a fluorine-based or a local molecular system, an adhesion-imparting agent such as an imidazole-based, a thiotriterpene-based, or a sand-system coupling agent, a phthalocyanine green, an iodine green, a diazo yellow, a coloring agent such as carbon black, etc. The curable resin formed on the substrate in the present invention The composition layer differs depending on the thickness of the inner layer circuit conductor layer, but is not particularly limited in terms of insulation reliability, etc., and is preferably 1 〇 1 to 150 μπι 左 preferably 15 to 80 μηι. The hardening treatment of the composition is usually a thermosetting treatment, which varies depending on the type of the curable resin, etc., but the curing temperature is generally ～200 ° C, and the curing time is generally 15 to 90 minutes. Further, the curing temperature is high. The hardening temperature is hardened in the stage, or hardened on the side, and the method of forming the hard fat composition layer on the substrate is used in the method of manufacturing the circuit board of the present invention from the viewpoint of preventing wrinkles on the surface of the formed insulating layer. Although it is not particularly limited, it is preferable to prepare a varnish formed from a solution or a dispersion of a curable resin composition, and the coating liquid (varnish) is applied onto a support film to be dried - -31 - 200904283 An adhesive film having a curable resin composition layer is applied, and the curable resin composition layer of the adhesive film is laminated on one surface or both surfaces of the substrate, and the support film is peeled off. The lamination is preferably carried out by vacuum lamination under reduced pressure. Further, the laminating method may be a batch type or a continuous type using a roll. The lamination conditions are preferably carried out by laminating under a reduced pressure of from 1 to llkgf/cm2 (9.8 χ 104 to 107.9 χ 104) and a pressure of 20 mmHg (26.7 hPa) or less. Further, the vacuum lamination can be carried out using a commercially available vacuum laminator, and the specific examples are as described above. Examples of the support film for the adhesive film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate and polyethylene naphthalate, and polycarbonates. A plastic film such as bismuth imide or a metal foil such as release paper, copper foil or aluminum foil. Further, the support film may be subjected to mold release treatment in addition to matting treatment or corona treatment. In the present invention, a prepreg may be used in the case where a curable resin composition layer is formed on the substrate as described above. The "prepreg" in the present invention means that the sheet-shaped reinforcing base material formed by weaving is impregnated with the curable resin composition by a hot melt method or a solvent method, and is semi-cured by heating. As the fiber of the sheet-like reinforcing substrate, for example, a glass cloth or an linalin fiber can be used as the fiber for the prepreg. The hot melt method does not dissolve the resin in an organic solvent, and once the resin is coated on a coated paper having good peelability from the resin, it is laminated on a sheet-like reinforcing substrate or coated by a mouth pattern. The cloth machine is directly coated or the like to produce a prepreg. Further, in the same manner as the adhesive film, the solvent method is a method in which a sheet-like reinforcing substrate is impregnated with a resin varnish in which a resin is dissolved in a solvent of -32-200904283, and the sheet-shaped reinforcing substrate is impregnated with a resin varnish and then dried. In the present invention, when a prepreg is used to manufacture a circuit substrate, if a single prepreg or a plurality of prepregs are overlapped, a multilayer prepreg is laminated, or by vacuum lamination. The prepreg of the surface layer of one or both of the laminates laminated on the substrate is laminated on the surface of the prepreg so that the metal film layer contacts the surface of the prepreg, and the film for transfer of the laminated metal film is superposed by heating When the prepreg is hardened by pressurization, the metal film layer of the film for metal film transfer adheres to the prepreg. Then, the support layer of the film for metal film transfer is peeled off, and the release layer existing on the metal film layer after removing the release support layer is dissolved in an aqueous solution to transfer the metal film layer to the prepreg. Further, a single prepreg or a plurality of prepregs are stacked, and a metal film transfer film is superposed thereon so that the metal film layer contacts the surface of the prepreg, and the wiring is buried by a vacuum hot press. And hardening, as described above, the support layer of the film for metal film transfer is peeled off, the release layer is removed, and the metal film layer can be transferred onto the prepreg. Further, in the same manner, on one or both sides of the multilayer prepreg in which a single prepreg or a plurality of prepregs are overlapped, the metallized layer is in contact with the surface of the prepreg, and the laminated metal is overlapped. The film for film transfer can be cured by heating and pressing to form a metal-clad laminate. The hardening treatment conditions of the prepreg, the dissolution and removal conditions of the aqueous solution of the water-soluble cellulose layer, the operation, and the like are as follows. When using a vacuum hot press, the conditions are generally preferably in the range of 5 to 20 kgf/cm2 (49·〇χ1〇4 to 196.1×10 4 N/m2), and the air pressure is 20 mmHg (-33-200904283 26.7 hPa). In the following decompression, from the viewpoint of preventing the formation of the metal film formed on the surface of the insulating layer, the curing is preferably performed while raising the temperature from room temperature to high temperature. When the circuit substrate is formed, the insulating layer formed on the substrate may be punched as needed to form a via hole or a through hole. The punching step may be carried out from the support after the hardening treatment, or may be carried out from the release layer after peeling off the support, or may be carried out from the metal film after removing the release layer. Punching can be performed, for example, by a well-known method such as a laser, a laser, or the like, and can be combined as needed, and the most common method of punching with a laser such as a carbon dioxide laser or a YAG laser. . After the punching step, the slag present at the bottom of the through hole or the like is removed by a desmear step. The desmear step is a well-known method such as a wet method such as a dry method such as plasma or an oxidizing agent such as an alkaline permanganic acid solution. When forming a circuit board, the conductor layer (wiring layer) is formed by using the metal film layer as a conductor layer as it is, or by electroless plating and/or electrolytic plating on the metal film layer to further form a metal layer. It grows to form a conductor layer. The metal layer of the electrolytic plating is usually a metal layer of the same metal type as the metal film layer, but a metal layer of a different metal type may be formed. As a suitable example, for example, when the metal film layer is a copper layer or a layer of a chromium layer or a nickel-chromium alloy layer is formed on the copper layer, copper plating is formed on the copper layer of the surface layer after transfer. The aspect of the layer. In the present invention, although the thickness of the electrolytic plating layer depends on the thickness of the metal film layer, the design of the circuit substrate is generally 3 to 35 μm, preferably 5 to 30 μm. Further, when the punching step is performed, a conductor layer can be formed in the hole by a combination of electroless plating and electrolytic plating or direct plating, as disclosed in Japanese Laid-Open Patent Publication No. Hei. The present invention is described in more detail below by way of examples, but the invention is not limited by the following examples. In the following description, "parts" means "parts by weight". [Example 1] <Production of film for metal film transfer> Coating of hydroxypropylmethylcellulose benzene by a die coater on a polyethylene terephthalate (hereinafter abbreviated as PET) film having a thickness of 38 μm Dimethyl ester ("HP-55" manufactured by Shin-Etsu Chemical Co., Ltd.) has a solid content of 10% methyl ethyl ketone (hereinafter referred to as MEK) and N,N-dimethylformamide (hereinafter referred to as DMF). The 1:1 solution was heated to room temperature at room temperature of 3 ° C / sec to 1 40 t using a hot air drying oven to remove the solvent, and hydroxypropyl methylcellulose phthalate was formed on the PET film. Ester layer. Next, a 500 nm copper layer was formed on the propyl cellulose phthalate layer by doping (Ε-400S, manufactured by Canon-Anelva Co., Ltd.), and a 20 nm chromium layer was formed on the copper layer. To produce a film for metal film transfer of a 520 nm metal film layer. <Production of Adhesive Film> In a mixture of 15 parts of MEK and 15 parts of cyclohexanone, 28 parts of liquid bisphenol A type epoxy resin was dissolved by heating while stirring (epoxy equivalent 180, Japanese ring) "Epicoat 828EL" manufactured by Oxygen Resin Co., Ltd. and 28 parts of naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, "Japan 4" by Dainippon Ink Chemicals - 35-200904283 Industrial Co., Ltd.). In this, 110 parts of a naphthol-based curing agent (hydroxyl equivalent 215, "Tosho Chemical Co., Ltd." "SN-485"), a solid component of 50% MEK solution, and 1 part of a hardening catalyst (four countries into a chemical industry) (2E4MZ)) 70 parts of spherical vermiculite (average particle size 0.5μπι, (stock) ADMATECHS system "SOC2"), 30 parts of polyvinyl butyral resin (Suizu Chemical Industry Co., Ltd.) "KS-1") A solid solution of 15% ethanol and a 1:1 solution of toluene was uniformly dispersed in a high-speed rotating mixer to prepare a resin varnish. The varnish was applied onto a PET film having a thickness of 38 μm by a die coater, and the solvent was removed using a hot air drying oven to prepare an adhesive film having a thickness of 40 μm of the curable resin composition layer. <Formation of a curable resin composition layer on a circuit board by an adhesive film> CZ8 100 (copper-containing copper misalignment) on a copper layer of a glass epoxy substrate on which a copper layer of 18 μm thick is formed A surface treatment agent (manufactured by MEC (manufactured by MEC)) of organic matter and organic acid is applied for roughening, and a batch type vacuum pressure laminator MVLP-500 is used in contact with the surface of the copper circuit. The brand name of the brand name is manufactured by laminating the adhesive film on both sides of the circuit board. The laminate was depressurized for 30 seconds and at a pressure of 13 hPa or less. Then, after cooling to room temperature, the support layer of the adhesive film is peeled off to form a layer of a curable resin composition on both surfaces of the circuit board. <Transfer metal film by film for metal film transfer> The film for metal film transfer of -36-200904283 is laminated on a circuit board so that the metal film layer contacts the curable resin composition layer . The lamination was carried out by laminating on both sides of a circuit board by using a batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Nihon Seiki Co., Ltd.). The lamination was pressure-reduced for 30 seconds, and the gas pressure was made 13 hPa or less, and then pressurized by a pressure of 30 seconds and 7.54 kgf/cm 2 . Thereafter, the curable resin composition layer was cured at 150 ° C for 30 minutes, and then cured at 180 ° C for 30 minutes to form an insulating layer (hardened layer). A PET film which is a support layer of the film for transfer of a metal film is peeled off from the insulating layer. The peelability is good and can be easily peeled off by hand. Then, the hydroxypropylmethylcellulose phthalate layer was dissolved and removed with a 1% aqueous sodium carbonate solution. The metal film layer was uniformly transferred. No abnormalities such as foaming between the resin and the metal layer, wrinkles of the metal layer, and cracking of the metal layer were observed. <Formation of copper plating layer> Electroless (electrolytic) copper plating was performed on the metal film layer to form a copper plating layer having a thickness of about SOgm to fabricate a multilayer printed wiring board. [Embodiment 2] <Production of Adhesive Film> In a mixture of 15 parts of MEK and 15 parts of cyclohexanone, 'dissolve 28 parts of liquid bisphenol A type epoxy resin (828EL) and 28 parts of naphthalene while stirring Type 4-functional epoxy resin (HP-4700). 50 parts of a phenolic curing agent, that is, a novolac resin containing a triple-trap structure (a phenolic hydroxyl equivalent of a solid matter of 1,200, "-37-200904283 LA7052" manufactured by Otsuka Ink Chemical Industry Co., Ltd." 20 parts of a solid component (MEK solution), 20 parts of a phenoxy resin (molecular weight: 50,000, a 40% solid solution of "E1256" manufactured by Nippon Epoxy Co., Ltd.), 0.1 part of a curing catalyst (2E4MZ), 55 parts of spherical vermiculite (SOC2), 30 parts of the polyvinyl butyral resin solution described in Example 1, and 3 parts of epoxy resin having a butadiene structure (molecular weight: 27,000, manufactured by DAICEL Chemical Industry Co., Ltd.) "PB-3600") is uniformly dispersed in a high-speed rotary mixer to produce a resin varnish. The varnish was applied onto a PET film having a thickness of 38 μm by a die coater, and a solvent was removed using a hot air drying oven to prepare an adhesive film having a thickness of 40 μm of the curable resin composition layer. <Formation of a curable resin composition layer on a circuit board by an adhesive film> CZ8 100 (copper-containing copper) on a copper layer of a glass epoxy substrate on which a copper layer of 18 μm thick is formed A complex type, an organic acid surface treatment agent (manufactured by MEC) is applied for roughening, and a batch type vacuum pressure laminator M VLP-5 00 is used in contact with the surface of the copper circuit. (The name of the product manufactured by Nihon Seiki Co., Ltd.), and an insulating adhesive resin film was laminated on both surfaces of the circuit board. The lamination was carried out under reduced pressure for 30 seconds at a gas pressure of 1 3 hPa or less. Then, after cooling to room temperature, the support layer of the adhesive film is peeled off, and a curable resin composition layer is formed on both surfaces of the circuit board. <Transfer metal film transfer by film for metal film transfer> The metal film layer is bonded to the insulating adhesive resin layer, and the film for metal film transfer of Example 1 is carried out by lamination-38-200904283 . The lamination was carried out by laminating on both surfaces of a circuit board by using a batch type vacuum pressure laminator MVLP-5 00 (trade name, manufactured by Nihon Seiki Co., Ltd.). The laminate was depressurized for 30 seconds, and the gas pressure was set to 13 hPa or less, followed by pressurization under a pressure of 30 seconds and 7.54 kgf/cm 2 . Thereafter, the curable resin composition layer was cured at 150 ° C for 30 minutes, and then cured at 180 ° C for 30 minutes to form an insulating layer (hardened layer). The support layer, that is, PET, is peeled off from the insulating layer. The peeling system is easily peeled off by hand. Then, the hydroxypropylmethylcellulose phthalate layer was dissolved and removed by a 1% aqueous sodium carbonate solution. The metal film layer was uniformly transferred, and no abnormality such as foaming between the resin and the metal layer, crepe of the metal layer, or cracking of the metal layer was observed. <Formation of Copper Plating Layer> Electroless (electrolytic) copper plating was performed on the metal film layer to form a copper plating layer having a thickness of about 3 μm to prepare a multilayer printed wiring board. [Example 3] <Production of Adhesive Film> A prepolymer of 30 parts of bisphenol quinone cyanide (cyanate equivalent 23 2, "BA23 0S75" manufactured by LONZA Japan Co., Ltd., and a MEK solution of 75% solid content) ) 10 parts of a phenol novolac type polyfunctional cyanate resin (cyanate equivalent 124, LONZA Japan Co., Ltd. "PT30"), and 4 parts of a naphthol type epoxy resin (epoxy equivalent 3 40, Dongkwa Chemicals Co., Ltd. "ESN-475V") 65% solid solution MEK solution, 5 parts -39- 200904283 liquid bisphenol A epoxy resin (8 2 8 EL ), 15 parts of phenoxy Resin solution (YP-70, manufactured by Tohto Kasei Co., Ltd., 1:1 solution of MEK and cyclohexanone with a solid content of 40%), and 4 parts of cobalt acesulfate (Π) as a hardening catalyst (Tokyo) A compound (stock) system, a solid component of 1% DMF solution, and 40 parts of spherical vermiculite (S0C2) were uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish. The varnish was applied onto a PET film having a thickness of 38 μm by a die coater, and a solvent was removed by using a hot air drying oven to prepare an adhesive film having a thickness of 40 μm of the curable resin composition layer. A curable resin composition layer was formed on the circuit board from the above-mentioned adhesive film by the same method as in the second embodiment. Then, in the same manner as in Example 2, the metal film was transferred onto the insulating layer through the film for metal film transfer described in Example 1, and copper plating layer was formed by electroless (electrolytic) copper plating. Make multilayer printed wiring boards. The peeling property of the support layer is good and can be easily peeled off by hand. Further, the metal film layer was uniformly transferred, and no abnormality such as foaming between the resin and the metal layer, wrinkles of the metal layer, or cracking of the metal layer was observed. [Example 4] <Preparation of modified polyimine> 'mix 50 g of G-3 000 (2 functional hydroxyl-terminated polybutadiene, number average molecular weight = 5〇47 (GPC method), hydroxyl equivalent = in the reaction vessel 1 798g/eq., solid content l〇〇w%: Japan Soda Co., Ltd., 23'5 g Ipz〇le 150 (aromatic hydrocarbon mixed solvent: Idemitic Petrochemical-40-200904283 (stock)) 0.02 g of dibutyltin laurate to dissolve evenly. When it became uniform, the temperature was raised to 50 ° C, and 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 8 7.08 g / eq.) was added while stirring, and the reaction was carried out for about 3 hours. Next, the reaction was cooled to room temperature, and then 8.83 g of benzophenonetetracarboxylic dianhydride (anhydride equivalent = 161.lg/eq.), 〇.〇7 g of triethylenediamine and 74.09 g of ethyl diglycol acetate (manufactured by DAICEL Chemical Industry Co., Ltd.) was heated to l3 ° C until stirring, and the reaction was carried out for about 4 hours. At the time point of confirming that the NCO peak of 22 5 0 CHT1 disappeared by FT-IR, 1.43 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 8 7.0 8 g/eq.) was further added, and then at 130 ° C The stirring reaction was carried out for 2 to 6 hours, and the disappearance of the NC peak was confirmed by FT-IR. The disappearance of the NC 0 peak was confirmed, and it was regarded as the end point of the reaction. After cooling to room temperature, it was filtered with a filter cloth of 1 〇 〇 mesh to obtain a modified polyimine resin. Properties of the modified polyimine resin: Viscosity = 7.0 Pa.s (25 ° C, E-type viscometer) Acid value = 6.9 mg KOH / g Solid content = 40 w% Number average molecular weight = 19,908 Polybutadiene structure Content rate = 50x 1 00 / ( 5〇 + 4.8 + 8.8 3 + 1.43 ) = 76.9 mass % <Production of Adhesive Film> 40 parts of the above modified polyimine resin varnish, 4 parts of liquid -41 - 200904283 bisphenol A type epoxy resin (828EL), 12 parts of dicyclopentylene Dilute polyfunctional epoxy resin (epoxy equivalent 279, "HP-7200H" manufactured by Dainippon Ink Chemicals Co., Ltd.), 8-5 parts of phenol novolac resin (phenolic hydroxyl equivalent of solid matter 1 2 0, large "TD-2090" manufactured by Nippon Ink Chemical Industry Co., Ltd., a 60% solid solution (MEK solution), and one part of spherical vermiculite (SOC2) were uniformly dispersed in a high-speed rotary mixer to produce a resin varnish. The varnish was applied onto a PET film having a thickness of 38 μm by a die coater, and a solvent was removed by using a hot air drying oven to prepare an adhesive film having a thickness of 40 μm of the curable resin composition layer. A curable resin composition layer was formed on the circuit board from the above-mentioned adhesive film by the same method as in the second embodiment. Then, by the same method as in Example 2, the metal film was transferred onto the insulating layer through the film for metal film transfer described in Example 1, and copper plating was formed by electroless (electrolytic) copper plating. Make multilayer printed wiring boards. The peeling property of the support layer is good and can be easily peeled off by hand. Further, the metal film layer was uniformly transferred, and no abnormality such as foaming between the resin and the metal layer, wrinkles of the metal layer, or cracking of the metal layer was observed. [Example 5] A multilayer printed wiring board was produced in the same manner as in Example 2 except that the metal film layer of the film for metal film transfer was composed of only a copper layer of 50 μm (no chromium layer). . The peeling property of the support layer is favorably peeled off by hand. Further, the metal film layer was uniformly transferred, and no abnormality such as foaming between the resin and the metal layer, wrinkles of the metal layer, or cracking of the metal layer was observed. -42 - 200904283 [Example 6] Multilayer printing was produced by the same method as in Example 2 except that the metal film layer of the film for metal film transfer was composed of only a 25 nm copper layer (a chromium-free layer). Wiring board. The peeling property of the support layer is favorably peeled off by hand. Further, the metal film layer was uniformly transferred, and no abnormality such as foaming between the resin and the metal layer, wrinkles of the metal layer, or cracking of the metal layer was observed. [Embodiment 7] <Production of Film for Metal Film Transfer> Plascoat Z-561 was applied by a die coater on a polyethylene terephthalate (hereinafter abbreviated as PET) film having a thickness of 38 μm. Chemical Industry Co., Ltd.) Solid content of 5% methyl ethyl ketone (hereinafter referred to as ΜΕΚ) and 1, Ν-dimethylformamide (hereinafter referred to as DMF) 1:1 solution 'drying with hot air The furnace is from room temperature to 1 2 0. (3 Let dry for 15 minutes to remove the solvent' to form a 1 μm water-soluble polyester resin layer on the PET film. Then 'sputter on the water-soluble polyester resin layer (Ε_400S, Canon-Anelva) A copper layer of 500 nm was formed, and a 20 nm chromium layer was formed on the copper layer to form a film for metal film transfer of a metal film layer of 520 nm. <Preparation of Adhesive Film> In a mixture of 15 parts of MEK and 15 parts of cyclohexanone, 28 parts of liquid bisphenol a type epoxy resin (epoxy equivalent) was heated and dissolved while stirring. 43- 200904283 180, "Epi coat 8 2 8EL" made by Japan Epoxy Resin Co., Ltd.) and 28 parts of naphthalene type 4-functional epoxy resin (epoxy equivalent 163, "HP4700" manufactured by Dainippon Ink Chemical Industry Co., Ltd. ). 50 parts of a phenolic curing agent, that is, a novolac resin containing a three-till structure (a phenolic hydroxyl equivalent of 120 for solids, "LA7052" manufactured by Dainippon Ink and Chemicals Co., Ltd., and a MEK solution of 60% solid content) 20 parts of phenoxy resin (molecular weight 50,000, "E 1 2 5 6" solid content 40% MEK solution made by Japan Epoxy Resin Co., Ltd.), 1 part of hardening catalyst (2E4MZ), 55 parts of sphere Vermiculite (SOC2) '30 parts of polyvinyl butyral resin ("KS-1" manufactured by Sekisui Chemical Co., Ltd.), 3 parts of epoxy resin with butadiene structure (molecular weight 27000, DAICEL Chemical Industry ( The "PB - 3 600" system was uniformly dispersed in a high-speed rotating mixer to produce a resin varnish. The varnish was applied onto a PET film having a thickness of 38 μm by a die coater, and the solvent was removed using a hot air drying oven to prepare an adhesive film having a thickness of 40 μm in the curable resin composition layer. <Formation of a curable resin composition layer on a circuit board by an adhesive film> CZ8100 (copper complex containing an azole) on a copper layer of a glass epoxy substrate on which a copper layer of 18 μm thick is formed A surface treatment agent (manufactured by MEC (manufactured by MEC)) of an organic acid is applied for roughening, and a batch type vacuum pressure laminating machine is used in a manner of contacting the surface of the copper circuit. 1^乂1^-5 〇 〇 (trade name, manufactured by Nihon Seiki Co., Ltd.), and the above-mentioned adhesive film was laminated on both surfaces of a circuit board. The laminate was depressurized for 30 seconds and at a pressure of 13 hPa or less. Next, after cooling to room temperature, the support layer of the adhesive film was peeled off, and a layer of a curable resin composition was formed on both surfaces of the circuit board. <Transfer metal film by film for metal film transfer> The film for metal film transfer is laminated on a circuit board so that the metal film layer contacts the curable resin composition layer. The lamination is carried out by laminating on both sides of a circuit board by using a batch type vacuum pressure laminator MVLP-5 00 (trade name, manufactured by Nihon Seiki Co., Ltd.). The lamination was pressure-reduced for 30 seconds, and the gas pressure was made 13 hPa or less, and then pressurized by a pressure of 30 seconds and 7.54 kgf/cm 2 . Thereafter, the curable resin composition layer was cured at 150 ° C for 30 minutes, and then hardened at 180 ° C for 30 minutes to form an insulating layer (hardened layer). A PET film which is a support layer of the film for transfer of a metal film is peeled off from the insulating layer. The peelability is good and can be easily peeled off by hand. Then, the water-soluble polyester layer was dissolved by dissolving in a 10% aqueous sodium hydroxide solution at 40 °C. The metal film layer was uniformly transferred, and no abnormality such as foaming between the resin and the metal layer, wrinkles of the metal layer, or cracking of the metal layer was observed. <Formation of copper plating layer> Electroless (electrolytic) copper plating was performed on the metal film layer to form a copper plating layer having a thickness of about 30 μm to fabricate a multilayer printed wiring board. [Embodiment 8] <Production of film for metal film transfer>
於厚度38μηι的聚對苯二甲酸乙二酯（以下簡稱PET -45- 200904283 )薄膜上，藉由口模式塗佈機來塗佈水溶性丙烯酸樹脂Coating a water-soluble acrylic resin on a polyethylene terephthalate (hereinafter referred to as PET-45-200904283) film having a thickness of 38 μm by a die coater
Joncryl 7600 ( B ASF日本（股）製，固體成分47%的水分 散品），使用熱風乾燥爐從室溫到120 °C使乾燥15分鐘以 去除溶劑，在P E T薄膜上形成1 μ m的水溶性丙烯酸樹脂 層。接著，於水溶性丙烯酸樹脂層上藉由濺鍍（E-4 00 S， Canon-Anelva (股）製）來形成5 0 0 nm的銅層，再於該銅 層上形成20nm的鉻層，以製作520nm的金屬膜層之金屬 膜轉印用薄膜。 <藉由黏著薄膜在電路基板上形成硬化性樹脂組成物層> 於以1 8 μιη厚的銅層形成電路的玻璃環氧樹脂基板之 銅層上，用CZ 8100 (含有唑類的銅錯合物、有機酸的表 面處理劑（MEC (股）製））來處理而施予粗化，以絕緣 性黏著樹脂薄膜接觸銅電路表面的方式，使用分批式真空 加壓層壓機MVLP-5〇0 ((股）名機製作所製商品名）， 將絕緣性黏著樹脂薄膜，即實施例7所製作的黏著薄膜層 壓於電路基板的兩面。層壓係減壓3 0秒，在1 3 h P a以下 的氣壓進行。接著，冷卻到室溫後，剝離黏著薄膜的支持 體層’在電路基板的兩面上形成硬化性樹脂組成物層。 <藉由金屬膜轉印用薄膜來轉印金屬膜> 以金屬膜層接觸絕緣性黏著樹脂層的方式，層合實施 例7所作成的金屬膜轉印用薄膜。層合係藉由使用分批式 真空加壓層壓機MVLP-5〇0 ((股）名機製作所製商品名 -46- 200904283 )，層壓於電路基板的兩面上而進行。層壓係減壓3 0秒 ，使氣壓成爲13hPa以下，然後藉由30秒、7.54kgf/cm2 的壓力下進行加壓而進行。之後，將硬化性樹脂組成物層 在150°C硬化30分鐘，再於180t硬化30分鐘，以形成絕 緣層（硬化物層）。由該絕緣層剝離支持體層即P E T。剝 離性係良好地以手能容易剝離。然後，以4(TC的1 0%氫氧 化鈉水溶液來溶解去除水溶性聚酯層。金屬膜層係被均勻 轉印，沒有見到樹脂與金屬層間的起泡、金屬層的皺紋、 金屬層的龜裂等異常。 <鍍銅層形成> 於金屬膜層上進行電（電解）鍍銅，形成約30μιη厚 的鍍銅層，以製作多層印刷配線板。 [實施例9] <金屬膜轉印用薄膜的製作> 於厚度38μιη的聚對苯二甲酸乙二酯（以下簡稱pet )薄膜上，藉由口模式塗佈機來塗佈水溶性丙烯酸樹脂 了〇1^1^1 3 54>1(8人8?日本（股）製，固體成分33.5°/。的水 溶液），使用熱風乾燥爐從室溫到1 20 °C使乾燥1 5分鐘以 去除溶劑，在P ET薄膜上形成1 μιη的水溶性丙烯酸樹脂 層。接著，於水溶性丙烯酸樹脂層上藉由濺鍍（E-400S， Canon-Anelva (股）製）來形成500nm的銅層，再於該銅 層上形成20nm的鉻層，以製作520nm的金屬膜層之金屬 -47- 200904283 膜轉印用薄膜。 <藉由黏著薄膜在電路基板上形成硬化性 於以18μπι厚的銅層形成電路的玻璃 銅層上，用 CZ8100(含有唑類的銅錯合 面處理劑（MEC (股）製））來處理而施 性黏著樹脂薄膜接觸銅電路表面的方式， 加壓層壓機MVLP-5 00 ((股）名機製作 將絕緣性黏著樹脂薄膜，即實施例7所製 壓於電路基板的兩面。層壓係減壓3 0秒 的氣壓進行。接著，冷卻到室溫後，剝離 體層，在電路基板的兩面上形成硬化性樹 <藉由金屬膜轉印用薄膜來轉印金屬膜> 以金屬膜層接觸絕緣性黏著樹脂層的 例7所作成的金屬膜轉印用薄膜。層合係 真空加壓層壓機MVLP-5 00 ((股）名機 )，層壓於電路基板的兩面上而進行。層 ，使氣壓成爲13hPa以下，然後藉由30 的壓力下進行加壓而進行。之後，將硬化 在1 5 0 °C硬化3 0分鐘，再於1 8 0 °C硬化3 0 緣層（硬化物層）。由該絕緣層剝離支持 離性係良好地以手能容易剝離。然後，以 化鈉水溶液來溶解去除水溶性聚酯層。金 樹脂組成物層> 環氧樹脂基板之 物、有機酸的表 予粗化，以絕緣 使用分批式真空 所製商品名）， 作的黏著薄膜層 ，在13hPa以下 黏著薄膜的支持 脂組成物層。 方式，層合實施 藉由使用分批式 製作所製商品名 壓係減壓3 0秒 秒、7.54kgf/cm2 性樹脂組成物層 分鐘，以形成絕 體層即PET。剝 4 0 °C的1 0 %氫氧 屬膜層係被均勻 -48- 200904283 轉印，沒有見到樹脂與金屬層間的起泡、金屬層的皺紋、 金屬層的龜裂等異常。 <鍍銅層形成> 於金屬膜層上進行電（電解）鍍銅’形成約30μ®厚 的鍍銅層，以製作多層印刷配線板。 [實施例10] <改性聚醯亞胺的調製> 於反應容器中，混合50克G-3000 (2官能性羥基末 端聚丁二烯，數量平均分子量=5047 ( GPC法），羥基當 量= 1 798 g/eq.，固體成分l〇〇w%:日本曹達（股）製）、 23.5克Ipzole 150 (芳香族烴系混合溶劑：出光石油化學 (珠）製）、0.007克月桂酸二丁錫’使均勻溶解。當變 成均句時，升溫到50 °C，再邊攪拌邊添加4_8克甲本-2,4-二異氰酸酯（異氰酸酯基當量=87.08 g/eq.) ’進行約3小 時的反應。接著，將此反應物冷卻到室溫爲止’然後於其 中加入 8.83克二苯甲酮四羧酸二酐（酸酐當量 = 161.1g/eq.) 、0.07克三伸乙二胺及74.09克乙基一甘酉学 醋酸酯（DAICEL化學工業（股）製）’邊攪拌邊升溫到 1 3 0。(：爲止，進行約4小時的反應。在以F T -1R確認 2250CHT1的NCO峰消失之時間點，更添加1.43克甲苯- 2,4-二異氰酸酯（異氰酸酯基當量=87.08§/叫.）’再於 1 3 0 °C邊進行2〜6小時的攪拌反應，邊以FT-IR來進行 -49 - 200904283 NCO峰消失的確認。確認NCO峰的消失，視爲反應的終 點，將其降溫到室溫爲止，然後以1 00網目的濾布來進行 過濾，得到改性聚醯亞胺樹脂。 改性聚醯亞胺樹脂的性質狀態： 黏度=7.0Pa‘s ( 25°c，E型黏度計） 酸價=6.9mgKOH/g 固體成分= 40w% 數量平均分子量=19890 聚丁二烯構造部分的含有率=5 0x 1 00/ ( 50 + 4·8 + 8.8 3 + 1 .43 ) =76.9 質量 ％ <黏著薄膜的製作> 4 0質量份的上述改性聚醯亞胺樹脂清漆、4份的液狀 雙酚Α型環氧樹脂（82 8EL )、12份的含有二環戊二烯之 多官能環氧樹脂（環氧當量279,大曰本油墨化學工業（ 股）製「HP-72 00H」）、8.5份的苯酚酚醛清漆樹脂（固 形物的酚性羥基當量1 2 0 ,大日本油墨化學工業（股）製 「TD-2090」，固體成分60%的MEK溶液）、及1〇份的 球形矽石（SOC2 )，在高速旋轉混合機中均勻分散，以 製作樹脂清漆。於厚度38μηι的PET薄膜上，藉由口模式 塗佈機來塗佈上述清漆’使用熱風乾燥爐來去除溶劑，製 作硬化性樹脂組成物層的厚度爲4 0 μιη的黏著薄膜。 藉由與實施例8同樣的方法，由上述黏著薄膜在電路 基板上形成硬化性樹脂組成物層。然後，藉由與實施例8 -50- 200904283 同樣的方法，經由實施例1記載的金屬膜轉印用薄膜，將 金屬膜轉印到絕緣層上’藉由電鍍銅來形成鍍銅層’以製 作多層印刷配線板。支持體層的剝離性係良好地以手能容 易剝離。又，金屬膜層係被均句轉印’沒有見到樹脂與金 屬層間的起泡、金屬層的皺紋、金屬層的龜裂等異常。 [實施例11] 除了金屬膜轉印用薄膜的金屬膜層係僅由5 00nm的銅 層所構成（無鉻層）以外’藉由與實施例8同樣的方法， 製作多層印刷配線板。支持體層的剝離性係良好地以手能 容易剝離。又，金屬膜層係被均勻轉印，沒有見到樹脂與 金屬層間的起泡、金屬層的皴紋、金屬層的龜裂等異常。 [實施例12] 除了金屬膜轉印用薄膜的金屬膜層係僅由25 Onm的銅 層所構成（無鉻層）以外，藉由與實施例8同樣的方法， 製作多層印刷配線板。支持體層的剝離性係良好地以手能 容易剝離。又，金屬膜層係被均勻轉印，沒有見到樹脂與 金屬層間的起泡、金屬層的皺紋、金屬層的龜裂等異常。 [實施例13] <金屬膜轉印用薄膜的製作> 於經醇酸系脫模劑所脫模處理的厚度3 8 μιη的pet薄 膜（LINTEC (股）製「AL-5」）之脫模處理面上，藉由 -51 - 200904283 口模式塗佈機來塗佈羥丙基甲基纖維素苯二甲酸酯（信越 化學工業（股）製「HP-55」）的固體成分10%之甲基乙 基酮（以下簡稱MEK)與Ν,Ν-二甲基甲醯胺（以下簡稱 DMF )的1 : 1溶液，使用熱風乾燥爐以3 t： /秒的升溫速 度從室溫升溫到1 4 0 °C爲止以去除溶劑，在p E T薄膜上形 成Ιμιη的羥丙基甲基纖維素苯二甲酸酯層。接著，於此羥 丙基纖維素苯二甲酸酯層上藉由濺鍍（E-400S，Canon-Anelva (股）製）來形成5〇OI1m的銅層，製作金屬膜轉印 用薄膜。使用該金屬膜轉印薄膜，藉由與實施例1同樣的 方法’製作多層印刷配線板。支持體層的剝離性係良好地 以手能容易剝離。又，金屬膜層係被均勻轉印，沒有見到 樹脂與金屬層間的起泡、金屬層的皺紋、金屬層的龜裂等 異常。 <導體層的剝離強度測定> 依照JIS C648 1來進行導體層的剝離強度測定。導體 厚係約3 0 μ m。 <絕緣層表面粗糙度測定> 絕緣層表面粗糙度的測定，係以銅蝕刻液或視需要以 鉻蝕刻液，去除所製作的多層印刷配線板上之鍍銅層及金 屬膜層，使用非接觸型表面粗糙度計（VEECO儀器製 WYKO NT3 3 00 )，以VSI接觸模式，50倍的透鏡，測定 範圍爲121μηιχ92μιη，求得絕緣層表面的Ra値（算術平 -52- 200904283 均粗糙度）。 <硬化後的金屬層狀態> 以目視來確認有沒有樹脂與金屬膜間的起泡、金屬膜 的皺紋、金屬膜的龜裂。將無不良時記錄爲〇’將有不良 時記錄其樣子。 <支持體層的剝離性的評價> 藉由以手來剝離支持體層，進行支持體層的剝離性之 評價。 [比較例1] 作爲具有脫模機能的支持體層，使用厚度50μηι的熱 塑性氟樹脂薄膜（ETFE :乙烯-三氟乙烯共聚物，東麗（ 股）製「Toyofuron」），進行與實施例1同樣的實驗。 即，在該熱塑性氟樹脂薄膜上藉由濺鍍（E-400S，Canon-Anelva (股）製）來形成500nm的銅層，再於該銅層上形 成20nm的銘層，以製作520nm的金屬膜層之金屬膜轉印 用薄膜，與實施例1同樣地，以該金屬膜轉印用薄膜的金 屬膜層接觸絕緣性黏著樹脂層的方式，層合於電路基板。 然後，將硬化性樹脂組成物層在1 5 (TC硬化3 0分鐘，再於 1 8 0°C硬化3 0分鐘，以形成絕緣層（硬化物層）。由透明 的熱塑性氟樹脂薄膜上來觀察，結果金屬膜層有許多皺紋 。又，熱塑性氟樹脂薄膜層的剝離性差，雖然以手剝離， -53- 200904283 但一部分的熱塑性氟樹脂薄膜未與金屬膜剝離而殘留，無 法完全剝離。 [比較例2] 使用具有蜜胺系脫模樹脂的厚度20 μιη之脫模PET薄 膜（（股）東麗薄膜加工製，「Finepeel」），進行與實 施例1同樣的實驗。即，在蜜胺系脫模樹脂層上藉由濺鍍 (E-400S, Canon-Anelva (股）製）來形成 500nm 的銅層 ，再於該銅層上形成20nm的鉻層，以製作520nm的金屬 膜層之金屬膜轉印用薄膜，與實施例1同樣地，以該金屬 膜轉印用薄膜的金屬膜層接觸絕緣性黏著樹脂層的方式， 層合於電路基板。然後，將硬化性樹脂組成物層在1 5 (TC 硬化30分鐘，再於180 °C硬化30分鐘，以形成絕緣層（ 硬化物層）。由透明的熱塑性氟樹脂薄膜上來觀察，結果 沒有見到樹脂與金屬膜間的起泡、金屬膜的皺紋' 金屬膜 的龜裂等異常。但是’ PET薄膜的剝離係困難。 [比較例3] 使用具有丙烯酸系脫模樹脂的厚度3 8 μ m之脫模p E T 薄膜（東麗薄膜加工（股）製，「Cerapeel HP2」）’進 行與實施例1同樣的實驗。即’在丙烯酸系脫模樹脂層上 藉由濺鍍（E-400S，Canon-Anelva (股）製）來形成 500nm的銅層，再於該銅層上形成20nm的鉻層，以製作 52 0nm的金屬膜層之金屬膜轉印用薄膜’與實施例1同樣 -54 - 200904283 地，以該金屬膜轉印用薄膜的金屬膜層接觸絕緣性黏著樹 脂層的方式，層合於電路基板。然後，將硬化性樹脂組成 物層在1 5 0 °C硬化3 0分鐘’再於1 8 0 °C硬化3 0分鐘’以形 成絕緣層（硬化物層）。由透明的PET薄膜上來觀察’結 果沒有見到樹脂與金屬膜間的起泡、金屬膜的皺紋、金屬 膜的龜裂等異常。但是，PET薄膜的剝離係困難。再者， PET薄膜上的丙烯酸系脫模樹脂係不溶解於水及鹼性水溶 液的任一者中。 [比較例4] 藉由口模式塗佈機，將聚乙烯醇（（股）KURARAY 製，「P V A - 2 0 3」）的固體成分1 5 %之乙醇與水的1 : 1溶 液塗佈在P E T薄膜上，使用熱風乾燥爐以3 °C /秒的升溫速 度從室溫升溫到1 4 0 °C爲止以去除溶劑，在p e T薄膜上形 成1 μ m的聚乙烯醇樹脂層。然後，進行與實施例1同樣的 實驗。即，於聚乙烯醇樹脂層上藉由濺鍍（E-400S， Canon-Anelva (股）製）來形成5〇〇nrn的銅層，再於該銅 層上形成20nm的鉻層’以製作52〇nm的金屬膜層之金屬 膜轉印用薄膜’與實施例1同樣地，以該金屬膜轉印用薄 膜的金屬膜層接觸絕緣性黏著樹脂層的方式，層合於電路 基板。然後，將硬化性樹脂組成物層在1 5 0 °C硬化3 0分鐘 ，再於1 8 0 C硬化3 0分鐘，以形成絕緣層（硬化物層）。 由透明的PET薄膜上來觀察’結果沒有見到樹脂與金屬膜 間的起泡、金屬膜的皺紋、金屬膜的龜裂等異常。但是’ -55 - 200904283 PET薄膜的剝離係困難。 下述表1〜3係實施例1〜1 3的評價結果，表4係比 較例1〜4的評價結果。 [表 1] __ 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 金屬膜的狀態 〇 〇 〇 〇 〇 〇 支持體層的剝離性 容易 容易 容易 容易 容易 容易 表面粗糙度(Ra)(nm) 50 60 30 70 60 50 剝離強度(kgf/cm) 0.8 0.9 0.6 1.3 1 0.9 [表2] 實施例7 實施例8 實施例9 實施例10 實施例11 實施例12 金屬膜的狀態 〇 〇 〇 〇 〇 〇 支持體層的剝離性 容易 容易 容易 容易 容易 容易 表面粗糙度(Ra)(nm) 50 50 50 70 60 55 剝離強度(kgf/cm) 0.7 0.8 0.7 1.2 0.9 0.8 [表3] 實施例13 金屬膜的狀態 〇 支持體層的剝離性 容易 表面粗糙度(Ra)(nm) 50 剝離強度(kgf/cm) 0.8 -56- 200904283 [表4] 比較例1 比較例2 比較例3 比較例4 金屬膜的狀態 有皺紋 〇 〇 〇 支持體層的剝離性 不良 不能 不能 不能 表面粗糙度(Ra)(nm) 剝離強度(kgf/cm) 編 - . • ※表中’ 「-」係指由於支持體層的剝離性不良或剝 離困難，而無法實施評價。 由表1〜3可知，依照本發明的金屬膜轉印用薄膜， 金屬膜層的轉印性（支持體層的剝離性）係良好，而且所 轉印的金屬膜層係具有良好的膜性質狀態。又，於電路基 板製造中’由於未將絕緣層（硬化性樹脂組成物的硬化層 )表面粗化，金屬膜層係以高的黏著力黏著在該絕緣層， 故在電路形成後藉由飩刻來去除不要的部分時也可容易地 去除’亦不易發生配線（導體層）的溶解等不良情況。另 一方面’以往的轉印薄膜，如表4所示地，即使可剝離支 持體層，也難以剝離，因此，在所轉印的金屬膜層中，容 易發生皺紋、剝落等的不良情況，而且亦有不能支持體層 的情況，爲缺乏實用性者。 [產業上的利用可能性] 本發明的金屬膜轉印用薄膜，由於可將沒有皴紋、龜 裂等而良好性質狀態的金屬膜層簡單地轉印到硬化性樹脂 組成物層上，故特別適用於電路基板的配線形成。 本申請案係以日本申請的特願2007-052054及特願 -57- 200904283 200 7 -2 1 63 03爲基礎，此等的內容係完全包含於本說明書 中〇Joncryl 7600 (B ASF Japan Co., Ltd., 47% solid dispersion of water), dried in a hot air drying oven from room temperature to 120 °C for 15 minutes to remove solvent and form 1 μm water-soluble on PET film. Acrylic resin layer. Next, a copper layer of 500 nm was formed on the water-soluble acrylic resin layer by sputtering (E-4 00 S, manufactured by Canon-Anelva Co., Ltd.), and a 20 nm chromium layer was formed on the copper layer. A film for metal film transfer of a metal film layer of 520 nm was produced. <Formation of a curable resin composition layer on a circuit board by an adhesive film> CZ 8100 (copper-containing copper) on a copper layer of a glass epoxy substrate on which a copper layer having a thickness of 18 μm is formed The complex compound and the surface treatment agent for organic acid (manufactured by MEC) are treated to be roughened, and the batch-type vacuum pressure laminator MVLP is used in such a manner that the insulating adhesive resin film contacts the surface of the copper circuit. -5〇0 (trade name manufactured by Nihon Seiki Co., Ltd.), an insulating adhesive resin film, that is, an adhesive film produced in Example 7 was laminated on both surfaces of a circuit board. The laminating pressure was reduced for 30 seconds, and the pressure was measured at a pressure of 1 3 h P a or less. Then, after cooling to room temperature, the support layer of the adhesive film is peeled off to form a curable resin composition layer on both surfaces of the circuit board. <Transfer metal film by film for metal film transfer> The film for metal film transfer of Example 7 was laminated so that the metal film layer contacted the insulating adhesive resin layer. The lamination was carried out by laminating on both sides of a circuit board by using a batch type vacuum pressure laminator MVLP-5〇0 (trade name: 46-200904283, manufactured by Nippon Seiki Co., Ltd.). The pressure was reduced for 30 seconds in the lamination, and the gas pressure was set to 13 hPa or less, and then pressurization was carried out under a pressure of 30 seconds and 7.54 kgf/cm 2 . Thereafter, the curable resin composition layer was cured at 150 ° C for 30 minutes and then at 180 t for 30 minutes to form an insulating layer (hardened layer). The support layer, that is, P E T is peeled off from the insulating layer. The peeling system is easily peeled off by hand. Then, 4 (TC of 10% aqueous sodium hydroxide solution was used to dissolve and remove the water-soluble polyester layer. The metal film layer was uniformly transferred, and no foaming between the resin and the metal layer, wrinkles of the metal layer, and metal layer were observed. Abnormality such as cracking. <Formation of copper plating layer> Electroless (electrolytic) copper plating was performed on the metal film layer to form a copper plating layer having a thickness of about 30 μm to produce a multilayer printed wiring board. [Embodiment 9] <Example 9] Preparation of Film for Metal Film Transfer> On a polyethylene terephthalate (hereinafter referred to as pet) film having a thickness of 38 μm, a water-soluble acrylic resin was applied by a die coater. 1 3 54 > 1 (8 persons 8? Japan (stock), solid solution 33.5 ° /.), using a hot air drying oven to dry at room temperature to 1 20 ° C for 15 minutes to remove the solvent, at P ET A water-soluble acrylic resin layer of 1 μm was formed on the film, and then a 500 nm copper layer was formed on the water-soluble acrylic resin layer by sputtering (E-400S, manufactured by Canon-Anelva Co., Ltd.), and the copper layer was further formed. Forming a 20nm chromium layer on the metal layer to make a 520nm metal film layer-47-200904283 A film is used to form a glass-copper layer which is formed of a copper layer having a thickness of 18 μm thick on a circuit board by an adhesive film, and CZ8100 (a copper-matched surface treatment agent containing an azole (MEC) )) The method of applying the adhesive resin film to the surface of the copper circuit, the pressure laminating machine MVLP-5 00 (made by the name machine), the insulating adhesive resin film, that is, the pressure on the circuit substrate The two sides of the laminate were pressure-reduced at a pressure of 30 seconds. Then, after cooling to room temperature, the body layer was peeled off to form a curable tree on both sides of the circuit substrate. The metal was transferred by a film for transfer of a metal film. Film> A film for metal film transfer which was obtained by contacting the insulating film layer with a metal film layer. The laminated vacuum pressure laminator MVLP-5 00 (manufacturing machine) was laminated. The layer is formed on both sides of the circuit board, and the gas pressure is 13 hPa or less, and then pressurization is performed under a pressure of 30. Thereafter, the hardening is performed at 150 ° C for 30 minutes, and then at 180 °. C hardened 3 0 edge layer (hardened layer). Stripped from the insulating layer The dispersing system is easily peeled off by hand. Then, the aqueous sodium polyester layer is dissolved and removed to remove the water-soluble polyester layer. The gold resin composition layer> The epoxy resin substrate and the organic acid are coarsened to the surface. The insulating film is made of a batch type vacuum, and the adhesive film layer is adhered to the supporting fat composition layer of the film at 13 hPa or less. The method of laminating is carried out by using a batch type product. The 0 second second, 7.54 kgf/cm2 resin composition layer was minute to form a permanent layer, namely PET. The 10% oxyhydrogen film layer stripped at 40 °C was uniformly transferred from -48 to 200904283, and no abnormalities such as foaming between the resin and the metal layer, wrinkles of the metal layer, and cracking of the metal layer were observed. <Formation of copper plating layer> Electroless (electrolytic) copper plating was performed on the metal film layer to form a copper plating layer of about 30 μ® thick to fabricate a multilayer printed wiring board. [Example 10] <Preparation of modified polyimine> In a reaction vessel, 50 g of G-3000 (2-functional hydroxyl-terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl group was mixed Equivalent = 1 798 g/eq., solid content l〇〇w%: manufactured by Japan Soda Co., 23.5 g Ipzole 150 (aromatic hydrocarbon mixed solvent: manufactured by Idemitsu Petrochemical (bead)), 0.007 g of lauric acid Dibutyltin' makes it evenly soluble. When the homogenous sentence was changed, the temperature was raised to 50 ° C, and 4-8 g of methyl-2,4-diisocyanate (isocyanate group equivalent = 87.08 g/eq.) was added while stirring to carry out a reaction for about 3 hours. Next, the reaction was cooled to room temperature. Then, 8.83 g of benzophenone tetracarboxylic dianhydride (anhydride equivalent = 161.1 g/eq.), 0.07 g of triethylenediamine and 74.09 g of ethyl group were added thereto. A glucosinolate (DAICEL Chemical Industry Co., Ltd.) was heated to 130 ° with stirring. (: The reaction was carried out for about 4 hours. When the NCO peak of 2250 CHT1 disappeared by FT-1R, the addition of 1.43 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 § / called.) was added. Further, the stirring reaction was carried out for 2 to 6 hours at 130 ° C, and the disappearance of the NCO peak was carried out by FT-IR at -49 - 200904283. The disappearance of the NCO peak was confirmed, and the end point of the reaction was regarded as the end point of the reaction, and the temperature was lowered to After room temperature, it is filtered with a filter cloth of 100 mesh to obtain a modified polyimine resin. The property state of the modified polyimide resin: viscosity = 7.0 Pa's (25 ° C, E-type viscosity) Acid value = 6.9 mg KOH / g Solid content = 40 w% Number average molecular weight = 19,890 Content of polybutadiene structural part = 5 0x 1 00 / ( 50 + 4 · 8 + 8.8 3 + 1.43 ) = 76.9 Mass % <Production of Adhesive Film> 40 parts by mass of the above modified polyimine resin varnish, 4 parts of liquid bisphenol quinone type epoxy resin (82 8EL ), 12 parts containing dicyclopentane Polyfunctional epoxy resin (epoxy equivalent 279, "HP-72 00H" manufactured by Otsuka Ink Chemical Industry Co., Ltd.), 8.5 parts of phenol novolac Paint resin (phenolic hydroxyl equivalent of solid content of 120%, "TD-2090" manufactured by Dainippon Ink Chemical Industry Co., Ltd., 60% MEK solution), and one part of spherical vermiculite (SOC2), The resin varnish was uniformly dispersed in a high-speed rotary mixer to form a resin varnish. The varnish was applied to a PET film having a thickness of 38 μm by a die coater. The hot air drying oven was used to remove the solvent to prepare a curable resin composition layer. The adhesive film having a thickness of 40 μm was formed on the circuit board by the adhesive film in the same manner as in Example 8. Then, the same manner as in Example 8-50-200904283 was carried out. In the film for metal film transfer described in the first embodiment, the metal film is transferred onto the insulating layer to form a copper-plated layer by electroplating copper to form a multilayer printed wiring board. The peelability of the support layer is good. The metal film layer is easily peeled off. Further, the metal film layer is uniformly transferred. "No foaming between the resin and the metal layer, wrinkles of the metal layer, cracking of the metal layer, or the like is observed. [Example 11] The metal film layer of the film for film transfer was formed of a copper layer of only 500 nm (no chromium layer). A multilayer printed wiring board was produced by the same method as in Example 8. The peelability of the support layer was excellent. Further, the metal film layer was uniformly transferred, and no abnormality such as foaming between the resin and the metal layer, crepe of the metal layer, cracking of the metal layer, or the like was observed. [Example 12] In addition to the metal film A multilayer printed wiring board was produced in the same manner as in Example 8 except that the metal film layer of the transfer film was composed of only a 25 nm copper layer (a chromium-free layer). The peeling property of the support layer is favorably peeled off by hand. Further, the metal film layer was uniformly transferred, and no abnormality such as foaming between the resin and the metal layer, wrinkles of the metal layer, or cracking of the metal layer was observed. [Example 13] <Production of film for metal film transfer> PET film ("AL-5" manufactured by LINTEC Co., Ltd.) having a thickness of 38 μm which was subjected to release treatment with an alkyd-based release agent On the release-treated surface, the solid content of hydroxypropylmethylcellulose phthalate ("HP-55" manufactured by Shin-Etsu Chemical Co., Ltd.) was applied by a -51 - 200904283 mouth mode coater. a 1:1 solution of methyl ethyl ketone (hereinafter referred to as MEK) and hydrazine, hydrazine-dimethylformamide (hereinafter referred to as DMF), using a hot air drying oven at a heating rate of 3 t: / sec from room temperature The solvent was removed by heating to 140 ° C, and a hydroxypropyl methylcellulose phthalate layer of Ιμη was formed on the p ET film. Next, a copper layer of 5 Å OI1m was formed by sputtering (E-400S, manufactured by Canon-Anelva Co., Ltd.) on the hydroxypropylcellulose phthalate layer to prepare a film for metal film transfer. Using this metal film transfer film, a multilayer printed wiring board was produced in the same manner as in Example 1. The peeling property of the support layer is good and can be easily peeled off by hand. Further, the metal film layer was uniformly transferred, and no abnormality such as foaming between the resin and the metal layer, wrinkles of the metal layer, or cracking of the metal layer was observed. <Measurement of Peel Strength of Conductor Layer> The peel strength of the conductor layer was measured in accordance with JIS C648 1. The conductor is about 30 μm thick. <Measurement of Surface Roughness of Insulating Layer> The surface roughness of the insulating layer is measured by using a copper etching solution or a chromium etching solution as needed to remove the copper plating layer and the metal film layer on the produced multilayer printed wiring board. Non-contact surface roughness meter (WYKO NT3 3 00 by VEECO instrument), in VSI contact mode, 50 times lens, measuring range is 121μηιχ92μιη, and the Ra値 of the surface of the insulating layer is obtained (arithmetic flat-52-200904283) ). <Metal layer state after hardening> The presence or absence of foaming between the resin and the metal film, wrinkles of the metal film, and cracking of the metal film were visually confirmed. When there is no defect, record it as 〇' When there is a defect, record it. <Evaluation of the peeling property of the support layer> The peeling property of the support layer was evaluated by peeling off the support layer by hand. [Comparative Example 1] A thermoplastic fluororesin film (ETFE: ethylene-trifluoroethylene copolymer, "Toyofuron" manufactured by Toray Industries, Inc.) having a thickness of 50 μm was used as the support layer having a mold release function, and the same procedure as in Example 1 was carried out. experiment of. Namely, a 500 nm copper layer was formed on the thermoplastic fluororesin film by sputtering (E-400S, manufactured by Canon-Anelva Co., Ltd.), and a 20 nm in-layer layer was formed on the copper layer to form a 520 nm metal. In the same manner as in the first embodiment, the film for metal film transfer of the film layer is laminated on the circuit board so that the metal film layer of the film for metal film transfer contacts the insulating adhesive resin layer. Then, the curable resin composition layer was cured at 15 (TC for 30 minutes, and then cured at 180 ° C for 30 minutes to form an insulating layer (hardened layer). Observed from a transparent thermoplastic fluororesin film As a result, the metal film layer has many wrinkles. Further, the thermoplastic fluororesin film layer has poor peelability, and although it is peeled off by hand, some of the thermoplastic fluororesin film is not peeled off from the metal film and remains, and cannot be completely peeled off. Example 2] The same experiment as in Example 1 was carried out using a release PET film having a thickness of 20 μm having a melamine-based release resin ("Finepeel" manufactured by Toray Film Co., Ltd.), that is, in the melamine system. On the release resin layer, a 500 nm copper layer was formed by sputtering (E-400S, manufactured by Canon-Anelva Co., Ltd.), and a 20 nm chromium layer was formed on the copper layer to form a metal of a 520 nm metal film layer. In the same manner as in the first embodiment, the film for film transfer is laminated on the circuit board so that the metal film layer of the film for metal film transfer contacts the insulating adhesive resin layer. Then, the curable resin composition layer is laminated. 1 5 (TC hardening 30 points The bell was further hardened at 180 ° C for 30 minutes to form an insulating layer (hardened layer). When observed from a transparent thermoplastic fluororesin film, no foaming between the resin and the metal film and wrinkles of the metal film were observed. The film was abnormally cracked, etc., but the peeling of the PET film was difficult. [Comparative Example 3] A release p ET film having a thickness of 38 μm having an acrylic release resin (manufactured by Toray Film Processing Co., Ltd.) was used. "Cerapeel HP2") was subjected to the same experiment as in Example 1. That is, a 500 nm copper layer was formed by sputtering (E-400S, manufactured by Canon-Anelva Co., Ltd.) on an acrylic release resin layer. A film for forming a metal film for forming a chromium film of 20 nm on the copper layer to form a metal film layer of 520 nm is the same as in the first embodiment - 54 - 200904283, and a metal film layer of the film for transfer of the metal film The method of contacting the insulating adhesive resin layer is laminated on the circuit substrate. Then, the hardened resin composition layer is hardened at 150 ° C for 30 minutes and then hardened at 180 ° C for 30 minutes to form an insulation. Layer (hardened layer). Comes from a transparent PET film As a result, no abnormality such as foaming between the resin and the metal film, wrinkles of the metal film, or cracking of the metal film was observed. However, peeling of the PET film was difficult. Further, the acrylic release resin on the PET film was It is not dissolved in any of water and an aqueous alkaline solution. [Comparative Example 4] Solid content of polyvinyl alcohol ("PVA - 2 0 3", manufactured by KURARAY) was prepared by a die coater. A 1:1 solution of 5% ethanol and water was applied to the PET film, and the solvent was removed by heating from room temperature to 140 °C at a heating rate of 3 ° C / sec using a hot air drying oven. A 1 μm layer of polyvinyl alcohol resin was formed thereon. Then, the same experiment as in Example 1 was carried out. That is, a 5 〇〇nrn copper layer was formed on the polyvinyl alcohol resin layer by sputtering (E-400S, manufactured by Canon-Anelva Co., Ltd.), and a 20 nm chrome layer was formed on the copper layer. In the same manner as in the first embodiment, the metal film layer of the film for metal film transfer is bonded to the circuit board so that the metal film layer of the film for metal film transfer contacts the insulating adhesive resin layer. Then, the curable resin composition layer was cured at 150 ° C for 30 minutes, and then cured at 180 ° C for 30 minutes to form an insulating layer (hardened layer). When observed from a transparent PET film, no abnormality such as foaming between the resin and the metal film, wrinkles of the metal film, and cracking of the metal film was observed. However, the peeling of the PET film was difficult. Tables 1 to 3 below are the evaluation results of Examples 1 to 1 3, and Table 4 is the evaluation results of Comparative Examples 1 to 4. [Table 1] __ Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 State of metal film 剥离 The release property of the support layer is easy and easy, easy and easy, and easy surface roughness (Ra) (nm) 50 60 30 70 60 50 Peel strength (kgf/cm) 0.8 0.9 0.6 1.3 1 0.9 [Table 2] Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 State of metal film 〇〇 The peeling property of the support layer is easy, easy, easy, easy, and easy. Surface roughness (Ra) (nm) 50 50 50 70 60 55 Peel strength (kgf/cm) 0.7 0.8 0.7 1.2 0.9 0.8 [Table 3] Example 13 State of metal film 剥离 Removability of support layer Easy surface roughness (Ra) (nm) 50 Peel strength (kgf/cm) 0.8 -56- 200904283 [Table 4] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Metal In the state of the film, the peeling property of the wrinkle ruthenium support layer is unavoidable. Surface roughness (Ra) (nm) Peel strength (kgf/cm) 编 - . * * In the table, '-' means the support layer Poor peelability or peeling is difficult Shi evaluation. As is apparent from Tables 1 to 3, according to the film for metal film transfer of the present invention, the transfer property of the metal film layer (peelability of the support layer) is good, and the transferred metal film layer has a good film property state. . Further, in the production of the circuit board, since the surface of the insulating layer (hardened layer of the curable resin composition) is not roughened, the metal film layer is adhered to the insulating layer with a high adhesive force, so that the circuit is formed by the crucible. When the unnecessary portion is removed, it is possible to easily remove the problem such as dissolution of the wiring (conductor layer). On the other hand, as shown in Table 4, the conventional transfer film is difficult to peel off even if the support layer is peeled off. Therefore, in the transferred metal film layer, defects such as wrinkles and peeling are likely to occur. There are also cases where the body layer cannot be supported, for those who lack practicality. [Industrial Applicability] The film for metal film transfer of the present invention can be easily transferred to a curable resin composition layer by a metal film layer having a good property without crepe or cracking. It is especially suitable for wiring formation of circuit boards. This application is based on Japanese Patent Application No. 2007-052054 and Japanese Patent Application No. -57-200904283 200 7 -2 1 63 03. These contents are fully incorporated in this specification.